Polymers and curable compositions

ABSTRACT

The present invention is concerned with a vinyl polymer having at least one group of the general formula (1) permolecule at the molecular chain terminus.
 
-Z-R—CR 1 ═CR 2 R 3    (1)
 
wherein Z represents an oxygen atom, a sulfur atom, a group of the formula NR′, R′ represents a univalent hydrocarbon group containing 1 to 20 carbon atoms, or a bivalent organic group containing 1 to 20 carbon atoms, and R represents a carbonyl group, a direct bond or a bivalent organic group containing 1 to 20 carbon atoms; R 1  and R 2  are the same or different and each represents a hydrogen atom or a univalent organic group containing 1 to 20 carbon atoms, and R 3  represents an organic group containing 1 to 20 carbon atoms. 
The present invention is further concerned with a curable composition comprising the above vinyl polymer.

TECHNICAL FIELD

The present invention relates to a vinyl polymer having a reactivefunctional group at a terminus and to a curable composition comprisingthe polymer.

BACKGROUND ART

It is known that a polymer having an alkenyl group at a molecular chainterminus undergoes crosslinking either by itself or in the presence of acuring agent such as a hydrosilyl-containing compound to give aheat-resistant, durable cured product. The main chain structure of sucha polymer, so far known, includes polyether series polymers such aspolyethylene oxide, polypropylene oxide, polytetramethylene oxide, etc.;hydrocarbon series polymers such as polybutadiene, polyisoprene,polychloroprene, polyisobutylene, etc., inclusive of hydrogenationproducts thereof; polyester series polymers such as polyethyleneterephthalate, polybutylene terephthalate, polycaprolactone, etc.; andpolysiloxane series polymers such as polydimethylsiloxane, among others,and these polymers have been used in various applications selectivelyaccording to the characteristics of the respective main chainstructures.

Vinyl polymers have several characteristics not shared by the abovevarious polymers, such as high weather-resistance, heat resistance, oilresistance and transparency, among others, and the use of the polymershaving side-chain alkenyl groups has been advocated in the field ofweather-resistant coatings (e.g. Japanese Kokai PublicationHei-3-277645; Japanese Kokai Publication Hei-7-0399).

However, alkenyl-terminated vinyl polymers cannot be easily producedand, therefore, have not been much employed on the industrial scene asyet.

Japanese Kokai Publication Hei-1-247403 discloses a process forproducing an acrylic polymer having an alkenyl group at both terminiwhich comprises using either an alkenyl group-containing dithiocarbamateor diallyl disulfide as the chain transfer agent.

Further, Japanese Kokai Publication Hei-6-211922 discloses a process forproducing an alkenyl group-terminated acrylic polymer which comprisespreparing a hydroxyl group-terminated acrylic polymer using a hydroxylgroup-containing polysulfide or an alcoholic compound as the chaintransfer agent in the first place and taking advantage of the reactivityof the hydroxyl group so introduced.

Meanwhile, curable compositions adapted to give rubber-like elasticproducts on curing have been used broadly in the field of adhesive,sealing and shock-absorbing materials. These compositions can be roughlyclassified by the mode of curing into the so-called moisture-curablecompositions which are stable in a sealed environment but cure in theatmosphere by absorbing its moisture even at room temperature to giverubber-like elastic products and those compositions which are adapted tocrosslink through hydrosilylation or the like reaction on exposure toheat.

However, by the above prior art technology, it is difficult to introducean alkenyl group into the polymer terminus with good reproducibility.Moreover, since the standard radical polymerization reaction is utilizedin these processes, there is the problem that the molecular weightdistribution (the ratio of weight average molecular weight to numberaverage molecular weight) of the product polymer is as broad as 2 ormore and, therefore, the viscosity of the polymer is high. In utilizingthe polymer as a sealant or an adhesive, for instance, such a highviscosity makes it difficult to handle the polymer and, moreover, afiller for reinforcement cannot be formulated in a sufficient amount.

It has also been found difficult to introduce a (meth)acryloyl group,which has radical polymerization activity, into a vinyl polymer which issynthesized by radical polymerization. Particularly, few compounds witha (meth) acryloyl group introduced into the oligomer terminus have sofar been successfully synthesized.

In many of photocurable compositions so far available, a low molecularcompound having a (meth)acryloyl group is employed. In such cases, theodor caused by vaporization of the unreacted low-boiling compound duringand after curing has been a serious problem. To avoid this trouble, anoligomer having a (meth)acryloyl group is employed. However, chieflyfrom synthetic points of view, such oligomers are limited toepoxy-acrylate, urethane-acrylate, polyester-acrylate and the likesystems. Moreover, oligomers having large molecular masses are notavailable. As a result, such compositions tend to give comparativelyhard cured products and do not give cured products having goodrubber-like elasticity.

In view of the above state of the art, the present invention has for itsobject to provide a vinyl polymer having a reactive functional group ata molecular chain terminus at a high rate and a curable compositioncomprising the polymer.

SUMMARY OF THE INVENTION

The present invention, therefore, is concerned with a vinyl polymerhaving at least one group of the general formula (1) per molecule at themolecular chain terminus.-Z-R—CR¹═CR²R³   (1)wherein Z represents an oxygen atom, a sulfur atom, a group of theformula NR′, R′ represents a univalent hydrocarbon group containing 1 to20 carbon atoms, or a bivalent organic group containing 1 to 20 carbonatoms, and R represents a carbonyl group, a direct bond or a bivalentorganic group containing 1 to 20 carbon atoms; R¹ and R²are the same ordifferent and each represents a hydrogen atom or a univalent organicgroup containing 1 to 20 carbon atoms, and R³ represents an organicgroup containing 1 to 20 carbon atoms.

The present invention is further concerned with a curable compositioncomprising the above vinyl polymer.

The present invention is now described in detail.

DISCLOSURE OF THE INVENTION

In this specification, this vinyl polymer having at least one group ofthe general formula (1) per molecule at the molecular chain terminus issometimes referred to as “polymer (I)”. The “organic group” is notparticularly restricted but is preferably a group comprising a carbonatom, a hydrogen atom and 0 to 2 oxygen atoms, more preferably ahydrocarbon group.

The polymer (I) will be described below in the first place.

<<Polymer (I)>>

<Explanation of the Group Represented by General Formula (1)>

The group of the general formula (1) is as described below.

Referring to the general formula (1) , R¹ and R² may be the same ordifferent and each represents a hydrogen atom or a univalent organicgroup containing 1 to 20 carbon atoms.

As specific examples of a univalent organic group containing 1 to 20carbon atoms, there may be mentioned the following:

—(CH₂) _(n)—CH₃, —CH(CH₃)—(CH₂) _(n)—CH₃, —CH(CH₂CH₃)—(CH₂) _(n)—CH₃,—CH(CH₂CH₃) ₂, —C(CH₃) ₂—(CH₂) _(n)—CH₃, —C(CH₃) (CH₂CH₃)—(CH₂)_(n)—CH₃, —C₆H₅, —C₆H₅(CH₃), —C₆H₅ (CH₃) ₂, —(CH₂) _(n)—C₆H₅, —(CH₂)_(n)—C₆H₅ (CH₃), —(CH₂) _(n)—C₆H₅(CH₃) ₂

(n being an integer of not less than 0 and the total number of carbonatoms in each group being not more than 20). Among the above groups,hydrogen, methyl and ethyl are preferred and hydrogen and methyl are themore preferred, with hydrogen being particularly preferred.

In the general formula (1), R³ represents a univalent organic groupcontaining 1 to 20 carbon atoms. The univalent organic group containing1 to 20 carbon atoms for R³ includes not only the above-mentionedunivalent organic groups containing 1 to 20 carbon atoms but alsoorganic groups containing unsaturated groups or those having an aromaticring. Preferred is an organic group such that, when the polymer (I) isformulated as a curable composition, the group of the general formula(1) may undergo crosslinking through a photodimerization orpolymerization reaction with good efficiency.

From this point of view, R³ is preferably an aryl group or a vinylgroup. In this specification, when R³ is an aryl group, the group of thegeneral formula (1) is sometimes referred to as a cinnamate group forconvenience's sake. By the same token, when R³ is a vinyl group, thegroup of the general formula (1) is sometimes referred to as aconjugated diene group.

The aryl group mentioned above may have a substituent. Thisunsubstituted or substituted aryl group is specifically a phenyl,biphenyl or naphthyl group optionally having 1-3 substituents such as analkyl group containing 1 to 4 carbon atoms, an alkoxy group containing 1to 4 carbon atoms, hydroxyl, phenoxy, amino (which may be mono- ordi-substituted by an alkyl group containing 1 to 4 carbon atoms),halogen, nitro, methylenedioxy, etc., and the substituents may be thesame or different.

The aryl group is not particularly restricted but includes the followinggroups, among others.

Phenyl, o-, m- or p-tolyl, o-, m- or p-ethylphenyl, o-, m- orp-propylphenyl, m- or p-cumyl, o-, m- or p-butylphenyl, m- orp-isobutylphenyl, m- or p-s-butylphenyl, m- or p-t-butylphenyl, 2,3-,2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenyl, mesityl, o-, m- orp-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m- or p-propoxyphenyl, m-or p-isopropoxyphenyl, o-, m- or p-butoxyphenyl, m- orp-isobutoxyphenyl, m- or p-s-butoxyphenyl, m- or p-t-butoxyphenyl, 2,3-,2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethoxyphenyl, o-, m- orp-hydroxyphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dihydroxyphenyl,3-hydroxy-4-methoxyphenyl, m- or p-phenoxyphenyl, o-, m- orp-aminophenyl, o-, m- or p-(N-methylamino)phenyl, o-, m- orp-(N,N-dimethylamino) phenyl, o-, m- or p-fluorophenyl, o-, m- orp-chlorophenyl, 2,4-dichlorophenyl, o-, m- or p-bromophenyl, o-, m- orp-nitrophenyl, 2,3- or 3,4-methylenedioxyphenyl, 2-, 3- or 4-biphenyland α-, β-naphthyl, among others. Particularly preferred is phenyl.

When R³ represents a vinyl group, this vinyl group may be substituted.Such a substituent includes the same univalent organic group containing1 to 20 carbon atoms as mentioned for R¹, R² and R³. The preferredexample of the unsubstituted or substituted vinyl group R³ is anunsubstituted vinyl group or a vinyl group having a methyl or ethyl as asubstutuent. Particularly preferred is a substituted vinyl group of theformula —CH═CH—CH₃.

Z in the general formula (1) represents an oxygen atom, a sulfur atom, agroup of the formula NR′ (where R′ represents a univalent organic groupcontaining 1 to 20 carbon atoms) or a bivalent organic group containing1 to 20 carbon atoms. Particularly preferred is an oxygen atom.

R in the general formula (1) represents a carbonyl group, a direct bondor a bivalent organic group of 1 to 20 carbon atoms. Particularlypreferred is a carbonyl group.

Therefore, the preferred species of the general formula (1) is thefollowing general formula (1′).—O—C(O)—CR¹═CR²R³   (1′)In the above formula, R¹, R² and R³ have the same meanings as definedabove.

If the number of groups represented by general formula (1) is less thanone on the average per mole of the polymer (I), a satisfactory curedproduct will not be obtained. In order to obtain a satisfactory curedproduct, the number of groups of the general formula (I) is preferably1.1 to 5 on the average, more preferably 1.2 to 4 on the average.

<Main Chain of Polymer (I)>

The monomer constituting the main chain of the polymer (I) is notparticularly restricted but may be any of various monomers. As examples,there may be mentioned (meth)acrylic monomers such as (meth)acrylicacid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate,isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl(meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate,n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl(meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl(meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate,2-aminoethyl (meth)acrylate, γ-(methacryloyloxypropyl) trimethoxysilane,(meth) acrylic acid-ethylene oxide adducts, trifluoromethylmethyl(meth)acrylate, 2-trifluoromethylethyl (meth)acrylate,2-perfluoroethylethyl (meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl(meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl(meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate,2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl(meth)acrylate and 2-perfluorohexadecylethyl (meth)acrylate; styrenicmonomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene,styrenesulfonic acid and salts thereof; fluorine-containing vinylmonomers such as perfluoroethylene, perfluoropropylene and vinylidenefluoride; silicon-containing vinyl monomers such asvinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleicacid and monoalkyl esters and dialkyl esters of maleic acid; fumaricacid and monoalkyl esters and dialkyl esters of fumaric acid; maleimidemonomers such as maleimide, methylmaleimide, ethylmaleimide,propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide,dodecylmaleimide, stearylmaleimide, phenylmaleimide andcyclohexylmaleimide; nitrile-containing vinyl monomers such asacrylonitrile and methacrylonitrile; amido-containing vinyl monomerssuch as acrylamide and methacrylamide; vinyl esters such as vinylacetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinylcinnamate; alkenes such as ethylene and propylene; conjugated dienessuch as butadiene and isoprene; vinyl chloride, vinylidene chloride,allyl chloride, allyl alcohol and so forth. These may be used singly ora plurality of them may be copolymerized. In the case ofcopolymerization, both random copolymerization and blockcopolymerization may be employed.

Preferred among these monomers, from the viewpoint of physicalproperties of products, among others, are (meth)acrylic monomers,acrylonitrile monomers, styrenic monomers, fluorine-containing vinylmonomers and silicon-containing vinyl monomers. More preferred areacrylic ester monomers and methacrylic ester monomers. Butyl acrylate isstill more preferred. In the practice of the present invention, thesepreferred monomers may be copolymerized with other monomers and, in suchcases, the content of these preferred monomers is preferably 40% byweight. The expression “(meth)acrylic acid”, for instance, so referredto hereinabove means “acrylic acid and/or methacrylic acid”.

The molecular weight distribution, namely the ratio (Mw/Mn) of weightaverage molecular weight (Mw) to number average molecular weight (Mn),of the polymer (I) is not particularly restricted. For facilitatinghandling by keeping the viscosity of the curable composition at a lowlevel while securing sufficient cured physical properties, however, anarrow molecular weight distribution is preferred. Preferred as themolecular weight distribution value is a value less than 1.8, morepreferably not more than 1.7, still more preferably not more than 1.6,yet more preferably not more than 1.5, still more preferably not morethan 1.4, most preferably not more than 1.3. The molecular weightdistribution is determined most commonly by gel permeationchromatography (GPC). The number average molecular weight and so on canbe determined on the polystyrene equivalent basis using chloroform orTHF as the mobile phase and polystyrene gel columns as columns.

The molecular weight of the polymer (I) is not particularly restrictedbut is preferably within the range of 500 to 100,000. At a molecularweight smaller than 500, the intrinsic characteristics of vinyl polymersare hardly manifested and, at above 100,000, the handling may becomedifficult in some instances.

<Polymerization>

The radical polymerization method which can be used for synthesizing thevinyl polymer of the present invention can be divided into the “generalradical polymerization method” in which a monomer having a givenfunctional group is simply copolymerized with a vinyl monomer using anazo or peroxide compound as the polymerization initiator and the“controlled radical polymerization method” which is capable ofintroducing a given functional group into a defined position such as theterminus.

The “general radical polymerization method” is an expedient method.However, by this method, a monomer having a given functional group isintroduced into the product polymer only in probabilities, and in orderto synthesize a polymer of high functionality, the particular monomermust be used in a fairly large amount. When conversely the amount of themonomer is small, the ratio of polymer molecules not provided with thegiven functional group is increased. Another disadvantage is that sincethe reaction is a free radical polymerization, the molecular weightdistribution is so broadened that only a polymer having a high viscositycan be obtained.

The “controlled radical polymerization method” can be divided into the“chain transfer agent technique” in which a vinyl polymer having afunctional group at the terminus is produced by carrying out thepolymerization using a chain transfer agent having a given functionalgroup, and the “living radical polymerization technique” in which thepolymerization proceeds with the growing chain terminus being constantly“growing” without being interrupted by a termination reaction to give apolymer approximating the designed molecular weight.

The “chain transfer agent technique” is capable of giving a polymer ofhigh functionality but a chain transfer agent having a given functionalgroup must be used in a fairly large amount relative to the initiator,with the consequent disadvantage in economics inclusive of the cost oftreatment involved. A further disadvantage of the technique is thatbecause it is also a free radical polymerization method as is said“general radical polymerization method, there can be obtained only apolymer having a broad molecular weight distribution and a highviscosity.

Unlike the above polymerization technology, the “living radicalpolymerization technique” is advantageous in that despite its also beinga method for radical polymerization which is generally considered to behardly controllable because of the high velocity of polymerization andhigh incidence of a termination reaction by radical-radical coupling orthe like, a termination reaction does not easily take place, thus givinga polymer with a narrow molecular weight distribution (Mw/Mn =about 1.1to 1.5), and further in that the molecular weight can be freelycontrolled by adjusting the monomer-initiator charge ratio.

Since “living radical polymerization” is thus capable of giving apolymer having a narrow molecular weight distribution profile and a lowviscosity and enables introduction of a monomer having a givenfunctional group in a more or less planned position, it is a furtherpreferred method for producing said vinyl polymer having a givenfunctional group according to the present invention.

In a narrow sense of the term, “living polymerization” means apolymerization in which the molecule chain grows with its growthterminus being constantly activated. Generally, however, the term isused to broadly cover as well a pseudo-living polymerization reaction inwhich the polymer grows while molecules with an activated terminus andmolecules with an inactivated terminus are in equilibrium, and the termas used in this specification also has the latter broad meaning.

Recently, “living radical polymerization” has been studied in earnest bymany research groups. By way of illustration, this technology includesthe method employing a cobalt porphyrin complex as described in J. Am.Chem. Soc., 116, 7943 (1994); the method using a radical capping agentor such as a nitroxide compoundas described in Macromolecules, 27, 7228(1994), and the atom transfer radical polymerization (ATRP) method usingan organohalogen compound as the initiator and a transition metalcomplex as the catalyst.

Among variations of “living radical polymerization”, the “atom transferradical polymerization”, which comprises polymerizing a vinyl monomer(s)using an organohalogen compound or a sulfonyl halide compound as theinitiator and a transition metal complex as the catalyst, isparticularly advantageous in that, in addition to the above-mentionedcharacteristics of “living radical polymerization”, it has a terminalhalogen or the like group, which is relatively advantageous forfunctional group conversion reactions, and affords a higher degree offreedom in initiator and catalyst design, hence it is more preferred asthe method of producing a vinyl polymer having a given functionalgroup(s). As specific references to this atom transfer radicalpolymerization, Matyjaszewski et al., J. Am. Chem. Soc., 1995, vol. 117,page 5614; Macromolecules, 1995, vol. 28, page 7901; Science, 1996, vol.272, page 866; WO 96/30421; WO 97/18247; and Sawamoto et al.,Macromolecules, 1995, vol. 28, page 1721, among others, can beconsulted.

In the practice of the invention, there is no particular limitation onwhich of these methods is employed. Basically, however, the controlledradical polymerization technique is utilized, and in consideration ofthe ease of reaction control, living radical polymerization is preferredand atom transfer radical polymerization is particularly preferred.

In the first place, the polymerization reaction utilizing a chaintransfer agent, which is one of controlled radical polymerization, isexplained. While the radical polymerization technique utilizing a chaintransfer agent (telomer) is not particularly restricted but for theproduction of a vinyl polymer having a terminal structure suited to thepresent invention, the following two alternative techniques, amongothers, can be mentioned.

These are the process for producing a halogen-terminated polymer using ahalogenated hydrocarbon as a chain transfer agent as described inJapanese Kokai Publication Hei-4-132706 and the process for producing ahydroxyl-terminated polymer using a hydroxyl-containing mercaptan, ahydroxyl-containing polysulfide or the like as the chain transfer agentas described in Japanese Kokai Publication Sho-61-271306, JapanesePatent 2594402, and Japanese Kokai Publication Sho-54-47782.

The living radical polymerization technique is now explained.

Among various versions of this technique, the process using a radicalcapping agent, such as a nitroxide compound, is first described. In thispolymerization, a nitroxy free radical (═N—O—), which is generallystable, is used as the radical capping agent. While such a compound isnot restricted, nitroxy free radicals from cyclic hydroxy amines, suchas the 2,2,6,6-substituted-1-piperidinyloxy radical and2,2,5,5-substituted-1-pyrrolidinyloxy radical, are preferred.Appropriate as the substituents are alkyl groups containing not morethan 4 carbon atoms, such as methyl and ethyl groups. Specific nitroxyfree radical compounds include but are not limited to the2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO),2,2,6,6-tetraethyl-1-piperidinyloxy radical,2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical,2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical,1,1,3,3-tetramethyl-2-isoindolinyloxy radical andN,N-di-tert-butylamine-oxy radical, among others. Such a stable freeradical as the galvinoxyl free radical may be used in lieu of thenitroxy free radical.

The above radical capping agent is used in combination with a radicalgenerator. It is presumable that the reaction product from a radicalcapping agent with a radical generator serve as a polymerizationinitiator to thereby proceed the polymerization of anaddition-polymerizable monomer(s). The mixing ratio of these two agentsis not particularly restricted but the radical initiator can beappropriately used in an amount of 0.1 to 10 moles per mole of theradical capping agent.

Although various compounds can be used as the radical generator, aperoxide capable of generating a radical under polymerizationtemperature conditions is preferred. Such peroxide includes but is notlimited to diacyl peroxides such as benzoyl peroxide and lauroylperoxide, dialkyl peroxides such as dicumyl peroxide and di-tert-butylperoxide, peroxydicarbonates such as diisopropyl peroxydicarbonate andbis (4-tert-butylcyclohexyl) peroxydicarbonate, alkyl peresters such astert-butyl peroxyoctoate and tert-butyl peroxybenzoate, and the like. Inparticular, benzoyl peroxide is preferred. Furthermore, a different kindof radical generator, for example a radical-generating azo compound suchas azobisisobutyronitrile, may be used in lieu of the peroxide.

As reported in Macromolecules, 1995, vol. 28, page 2993, suchalkoxyamine compounds as shown below may be used as the initiatorinstead of the combined use of a radical capping agent and a radicalgenerator.

When an alkoxyamine compound is used as the initiator and the verycompound has a hydroxyl or like functional group, as indicated by eitherformula shown above, a functional group-terminated polymer is obtained.By applying this principle to the method of the invention, a functionalgroup-terminated polymer can be provided.

The monomer(s) and the polymerization conditions, such as solvent andpolymerization temperature, to be used in the polymerization reactionusing a radical capping agent such as a nitroxide compound as mentionedabove are not particularly restricted but may be the same as those usedin the atom transfer radical polymerization reaction to be describedbelow.

The technique of atom transfer radical polymerization, which is a morepreferred version of the technique of living radical polymerizationaccording to the invention, is now described.

In this atom transfer radical polymerization, an organohalogen compound,in particular an organohalogen compound having a highly reactivecarbon-halogen bond (e.g. a carbonyl compound having a halogen at the aposition, or a compound having a halogen at the benzyl position), or asulfonyl halide compound or the like is preferably used as theinitiator.

Specific examples thereof are:

-   -   C₆H₅—CH₂X, C₆H₅—C(H) (X)CH₃, C₆H₅—C(X) (CH₃) ₂    -    (in the above formulas, C₆H₅ denotes a phenylene group and X        represents a chlorine, bromine or iodine atom),    -   R²⁵—C (H) (X)—CO₂R²⁶, R²⁵—C(CH₃) (X)—CO₂R²⁶, R²⁵—C (H)        (X)—C(O)R²⁶,    -   R²⁵—C(CH₃) (X) —C (O) R²⁶    -    (in the above formulas, R²⁵ and R²⁶ may be the same or        different and each represents a hydrogen atom or a C₁₋₂₀ alkyl        group, aryl group or aralkyl group and X represents a chlorine,        bromine or iodine atom),    -   R²⁵-C₆H₄—SO₂X    -    (in the above formulas, R²⁵ represents a hydrogen atom or a        C₁₋₂₀ alkyl group, aryl group or aralkyl group and X represents        a chlorine, bromine or iodine atom).

As the initiator for living radical polymerization, an organohalogen orsulfonyl halide compound having a functional group other than thefunctional group in charge of initiation of polymerization can also beemployed. In such cases, there is produced a vinyl polymer having thefunctional group in question at one main chain terminus and a halogengroup at the other main chain terminus. As such functional groups, therecan be mentioned alkenyl, crosslinking silyl, hydroxyl, epoxy, amino andamido groups, among others, can be mentioned.

The alkenyl-containing organohalogen compound is not particularlyrestricted but includes, among others, compounds having the structurerepresented by the general formula (8):R⁸R⁹C(X)—R¹⁰-R¹¹—C(R⁷)═CH₂   (8)wherein R⁷ represents an organic group containing 1 to 20 carbon atoms,preferably a hydrogen atom or a methyl group; R⁸ and R⁹ each representsa hydrogen atom, a univalent C₁₋₂₀ alkyl, aryl or aralkyl group; or theyare linked together at the respective free termini; R¹⁰ represents—C(O)O—(ester group), —C(O)— (keto group) or an o-, m- or p-phenylenegroup; R¹¹ represents a direct bond or a bivalent C₁₋₂₀ organic groupoptionally containing one or more ether linkages and X represents achlorine, bromine or iodine atom.

As specific examples of the substituents R⁸ and R⁹, there can bementioned hydrogen, methyl, ethyl, n-propyl, isopropyl, butyl, pentyland hexyl, among others. R⁸ and R⁹ may be joined to each other at therespective free termini to form a cyclic structure.

As specific examples of the alkenyl-containing organohalogen compoundrepresented by the general formula (8) there may be mentioned thefollowing:

-   -   XCH₂C(O)O(CH₂)_(n)CH═CH₂, H₃CC (H) (X)C(O)O(CH₂)_(n)CH═CH₂,        (H₃C) ₂C (X)C(O)O(CH₂)_(n)CH═CH₂, CH₃CH₂C(H)        (X)C(O)O(CH₂)_(n)CH═CH₂,        (in the above formulas, X represents a chlorine, bromine or        iodine atom and n represents an integer of 0 to 20), XCH₂C        (O)O(CH₂) _(n)O(CH₂)_(m)CH═CH₂, H₃CC(H) (X)C(O)O(CH₂) _(n)O(CH₂)        _(m)CH═CH₂, (H₃C) ₂C(X)C(O)O(CH₂) _(n)O(CH₂) _(m)CH═CH₂,        CH₃CH₂C(H) (X)C(O)O(CH₂) _(n)O(CH₂) _(m)CH═CH₂,    -    (in the above formulas, X represents. a chlorine, bromine or        iodine atom, n represents an integer of 1 to 20 and m represents        an integer of 0 to 20),    -   o-, m-, p-XCH₂—C₆H₄—(CH₂) _(n)—CH═CH₂, o-, m-, p-CH₃C(H)        (X)—C₆H₄—(CH₂) _(n)—CH═CH₂, o-, m-, p-CH₃CH₂C (H) (X)-C₆H₄—(CH₂)        _(n)—CH═CH₂    -    (in the above formulas, X represents a chlorine, bromine or        iodine atom and n represents an integer of 0 to 20),    -   o-, m-, p-XCH₂—C₆H₄—(CH₂) _(n)—O—(CH₂) _(m)—CH═CH₂, o-, m-,        p-CH₃C (H) (X)-C₆H₄—(CH₂) _(n)—O—(CH₂) _(m)—CH═CH₂, o-, m-,        p-CH₃CH₂C (H) (X)-C₆H₄—(CH₂) _(n)—O—(CH₂) _(m)—CH═CH₂    -    (in the above formulas, X represents a chlorine, bromine or        iodine atom, n represents an integer of 1 to 20 and m represents        an integer of 0 to 20),    -   o-, m-, p-XCH₂—C₆H₄—O—(CH₂)_(n)—CH═CH₂, o-, m-, p-CH₃C (H) (X)        -C₆H₄—O—(CH₂)_(n)—CH═CH₂, o-, m-, p-CH₃CH₂C (H)        (X)-C₆H₄—O—(CH₂)_(n)—CH═CH₂    -    (in the above formulas, X represents a chlorine, bromine or        iodine atom and n represents an integer of 0 to 20)    -   o-, m-, p-XCH₂—C₆H₄—O—(CH₂) _(n)—O—(CH₂) _(m)—CH═CH₂, o-, m-,        p-CH₃C (H) (X) -C₆H₄—O—(CH₂) _(n)—O—(CH₂) _(m)—CH═CH₂, o-, m-,        p-CH₃CH₂C (H) (X) -C₆H₄—O—(CH₂) _(n)—O—(CH₂) _(m)—CH═CH₂    -    (in the above formulas, X represents a chlorine, bromine or        iodine atom, n represents an integer of 1 to 20 and m represents        an integer of 0 to 20).

As the alkenyl-containing organohalogen compound, there may further bementioned compounds represented by the general formula (9):H₂C═C(R⁷)-R¹¹—C(R⁸) (X)-R¹²-R⁹   (9)wherein R⁷, R⁸, R⁹, R¹¹ and X are as defined above and R¹² represents adirect bond, —C(O)O— (ester group), —C(O)— (keto group) or an o-, m- orp-phenylene group.

R¹¹ is a direct bond or a bivalent organic group containing 1 to 20carbon atoms (which may contain one or more ether linkages) and, when itis a direct bond, the vinyl group is bound to the carbon atom to whichthe halogen atom is bound, giving an allyl halide compound. In thiscase, the carbon-halogen bond is activated by the neighboring vinylgroup and, therefore, R¹² is not always required to be a C(O)O group, aphenylene group or the like but may be a direct bond. In cases where R¹¹is not a direct bond, R¹²is preferably a C(O)O, C(O) or phenylene groupso that the carbon-halogen bond may be activated.

The compound of the above general formula (9) specifically includes,among others, the following compounds:

-   -   CH₂═CHCH₂X, CH₂═C (CH₃) CH₂X, CH₂═CHC(H) (X)CH₃, CH₂═C(CH₃)C(H)        (X)CH₃, CH₂═CHC(X) (CH₃) ₂, CH₂═CHC(H) (X)C₂H₅, CH₂═CHC (H)        (X)CH(CH₃) ₂, CH₂═CHC (H) (X)C₆H₅, CH₂═CHC (H) (X)CH₂C₆H₅,        CH₂═CHCH₂C (H) (X)-CO₂R, CH₂═CH(CH₂)₂C(H) (X)-CO₂R, CH₂═CH(CH₂)        ₃C (H) (X)-CO₂R, CH₂═CH(CH₂)₈C(H) (X)-CO₂R, CH₂═CHCH₂C (H)        (X)-C₆H₅, CH₂═CH(CH₂)₂C(H) (X)-C₆H₅, CH₂═CH(CH₂)₃C(H) (X)-C₆H₅    -    (in the above formulas, X represents a chlorine, bromine or        iodine atom and R represents a C₁₋₂₀ alkyl group, aryl group or        aralkyl group).

The alkenyl-containing sulfonyl halide compound specifically includes,among others, the following compounds:

-   -   o-, m-, p-CH₂═CH—(CH₂)_(n)—C₆H₄—SO₂X, o-, m-,        p-CH₂═CH—(CH₂)_(n)—O—C₆H₄—SO₂X    -    (in the above formulas, X represents a chlorine, bromine or        iodine atom and n represents an integer of 0 to 20).

The above crosslinking silyl-containing organohalogen compound includesbut is not limited to compounds having a structure represented by thegeneral formula (10):R⁸R⁹C (X)-R¹⁰-R¹¹—C (H) (R⁷)CH₂—[Si(R¹³)_(2−b)(Y) _(b)O]_(m)—Si(R¹⁴)_(3−a)(Y)_(a)   (10)wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, and X are as defined above; R¹³ and R¹⁴each represents a C₁₋₂₀ alkyl, aryl or aralkyl group or atriorganosiloxy group of the formula (R′)₃SiO— (in which R′ is aunivalent hydrocarbon group containing 1˜20 carbon atoms and the threeR' groups may be the same or different) and, when two or more R¹³ or R¹⁴groups are present, they may be the same or different; Y represents ahydroxyl group or a hydrolyzable group and, when two or more Y groupsare present, they may be the same or different; a represents 0, 1, 2 or3; b represents 0, 1 or 2; and m is an integer of 0 to 19, with thecondition that the relation a+bm24 1 should be satisfied.

Specific examples of the compound of the general formula (10) are:

-   -   XCH₂C(O)O(CH₂) _(n)Si (OCH₃) ₃, CH₃C(H) (X)C(O)O(CH₂)_(n)Si        (OCH₃)₃, (CH₃) ₂C(X)C(O)O(CH₂) _(n)Si(OCH₃) ₃,        XCH₂C(O)O(CH₂)_(n)Si(CH₃) (OCH₃) ₂, CH₃C(H) (X)C(O)O(CH₂)        _(n)Si(CH₃) (OCH₃) ₂, (CH₃)₂C(X)C(O)O(CH₂) _(n)Si(CH₃) (OCH₃) ₂,    -    (in the above formulas, X is a chlorine, bromine or iodine atom        and n is an integer of 0 to 20);    -   XCH₂C(O)O(CH₂) _(n)O(CH₂) _(m)Si(OCH₃) ₃, H₃CC(H) (X)C(O)O(CH₂)        _(n)O(CH₂) _(m)Si(OCH₃) ₃, (H₃C)₂C(X)C(O)O(CH₂) _(n)O(CH₂)        _(m)Si(OCH₃) ₃, CH₃CH₂C(H) (X)C(O)O(CH₂) _(n)O(CH₂) _(m)Si(OCH₃)        ₃, XCH₂C(O)O(CH₂) _(n)O(CH₂) _(m)Si(CH₃) (OCH₃) ₂, H₃CC(H)        (X)C(O)O(CH₂) _(n)O(CH₂) _(m)—Si(CH₃) (OCH₃) ₂,        (H₃C)₂C(X)C(O)O(CH₂) _(n)O(CH₂) _(m)—Si(CH₃) (OCH₃) ₂,        CH₃CH₂C(H) (X)C(O)O(CH₂) _(n)O(CH₂) _(m)—Si(CH₃) (OCH₃)₂,    -    (in the above formulas, X is a chlorine, bromine or iodine        atom; n is an integer of 1 to 20; and m is an integer of 0 to        20)    -   o, m, p-XCH₂—C₆H₄—(CH₂)₂Si(OCH₃)₃, o, m, p-CH₃C(H)        (X)-C₆H₄—(CH₂) ₂Si (OCH₃) ₃, o, m, p-CH₃CH₂C(H) (X)-C₆H₄—(CH₂)        ₂Si(OCH₃) ₃, o, m, p-XCH₂—C₆H₄—(CH₂) ₃Si (OCH₃)₃, o, m,        p-CH₃C(H) (X)-C₆H₄—(CH₂) ₃Si(OCH₃)₃, o, m, p-CH₃CH₂C(H)        (X)-C₆H₄—(CH₂) ₃Si(OCH₃)₃, o, m, p-XCH₂—C₆H₄—(CH₂) _(2—O—(CH) ₂)        ₃Si (OCH₃) ₃, o, m, p-CH₃C(H) (X) -C₆H₄—(CH₂)_(2—O—(CH) ₂)        ₃Si(OCH₃)₃, o, m, p-CH₃CH₂C(H) (X)-C₆H₄—(CH₂) ₂—O—(CH₂)        ₃Si(OCH₃)₃, o, m, p-XCH₂—C₆H₄—O—(CH₂) ₃Si(OCH₃)₃, o, m,        p-CH₃C (H) (X)-C₆H₄—O—(CH₂) ₃Si(OCH₃) ₃, o, m, p-CH₃CH₂C(H)        (X)-C₆H₄—O—(CH₂) ₃Si(OCH₃) ₃, o, m, p-XCH₂—C₆H₄—O—(CH₂)        ₂—O—(CH₂) ₃—Si (OCH₃) ₃, o, m, p-CH₃C(H)        (X)-C₆H₄—O—(CH₂)₂—O—(CH₂) ₃—Si(OCH₃)₃, and o, m, p-CH₃CH₂C(H)        (X)-C₆H₄—O—(CH₂) ₂—O—(CH₂) ₃Si(OCH₃) ₃,    -    (in the above formulas, X is a chlorine, bromine or iodine        atom) among others.

As further examples of the crosslinking silyl-containing organohalogencompound, there may be mentioned compounds having a structurerepresented by the general formula (11):(R¹⁴) _(3-a)(Y)_(a)Si—[OSi(R¹³) _(2-b)(Y) _(b)]_(m)—CH₂—C(H) (R⁷)-R¹¹—C(R⁸) (X)-R¹²-R⁹   (11)wherein R⁷, R⁸, R⁹, R¹¹, R¹², R¹³, R¹⁴, a, b, m, X and Y are as definedabove.

Specific examples of such compound are as follows: (CH₃O) ₃SiCH₂CH₂C(H)(X) C₆H₅, (CH₃O) ₂(CH₃)SiCH₂CH₂C(H) (X)C₆H₅, (CH₃O) ₃Si(CH₂) ₂C(H)(X)-CO₂R, (CH₃O) ₂(CH₃)Si(CH₂) ₂C(H) (X)-CO₂R, (CH₃O) ₃Si(CH₂) ₃C(H)(X)-CO₂R, (CH₃O) ₂(CH₃)Si(CH₂) ₃C(H) (X)-CO₂R, (CH₃O) ₃Si(CH₂) ₄C(H)(X)-CO₂R, (CH₃O) ₂(CH₃)Si(CH₂) ₄C(H) (X)-CO₂R, (CH₃O) ₃Si(CH₂) ₉C(H)(X)-CO₂R, (CH₃O) ₂(CH₃)Si(CH₂) ₉C(H) (X)-CO₂R, (CH₃O) ₃Si(CH₂) ₃C(H)(X)-C₆H₅, (CH₃O) ₂(CH₃)Si(CH₂)₃C(H) (X)-C₆H₅, (CH₃O) ₃Si(CH₂) ₄C(H)(X)-C₆H₅, and (CH₃O) ₂(CH₃)Si(CH₂) ₄C(H) (X)-C₆H₅,

-   -   (in the above formulas, X is a chlorine, bromine or iodine atom        and R is a C₁₋₂₀ alkyl, aryl or aralkyl group) , among others.

The hydroxyl-containing organohalogen compound or sulfonyl halidecompound is not particularly restricted but may be a compound in thefollowing:HO—(CH₂)—OC(O)C(H) (R) (X)wherein X is a chlorine, bromine or iodine atom; R is a hydrogen atom ora C₁₋₂₀ alkyl, aryl or aralkyl group; and n is an integer of 1 to 20.

The amino-containing organohalogen compound or sulfonyl halide compoundis not particularly restricted but may be a compound in the following:H₂N—(CH₂)_(n)—OC(O)C(H) (R) (X)wherein X is a chlorine, bromine or iodine atom; R is a hydrogen atom ora C₁₋₂₀ alkyl, aryl or aralkyl group;. and n is an integer of 1 to 20.

The epoxy-containing organohalogen compound or sulfonyl halide compoundis not particularly restricted but may be a compound in the following:

wherein X is a chlorine, bromine or iodine atom; R is a hydrogen atom ora C₁₋₂₀ alkyl, aryl or aralkyl group; and n is an integer of 1 to 20.

For obtaining a vinyl polymer by this polymerization method, anorganohalogen compound or sulfonyl halide compound having two or moreinitiation sites can be used as the initiator to obtain a polymer havingtwo growing termini. Specific examples thereof are:

-   -   o-, m- or p-XCH₂—C₆H₄—CH₂X, o-, m-or p-CH₃C(H) (X)-C₆H₄—C(H)        (X)CH₃, o-, m- or p-(CH₃)₂C(X)-C₆H₄—C(X) (CH₃) ₂    -    (in the above formulas, C₆H₄ denotes a phenylene group and X        represents a chlorine, bromine or iodine atom),    -   RO₂C—C (H) (X)-(CH₂)_(n)—C(H) (X)-CO₂R, RO₂C—C(CH₃) (x)-(CH₂)        _(n)—C(CH₃) (X)-CO₂R, RC(O)—C(H) (X)-(CH₂)_(n)—C(H) (X)-C(O)R,        RC(O)—C(CH₃) (X)-(CH₂)_(n)—C(CH₃) (X)-C(O)R    -    (in the above formulas, R represents a C₁₋₂₀ alkyl group; aryl        group or aralkyl group; n represents an integer of 0 to 20; and        X represents a chlorine, bromine or iodine atom),    -   XCH₂—C(O)—CH₂X, H₃C—C(H) (X)-C(O)—C(H) (X)-CH₃, (H₃C)₂C(X)-C        (O)—C(X) (CH₃) ₂, C₆H₅C(H) (X)-(CH₂)_(n)—C(H) (X)C₆H₅    -    (in the above formulas, X represents a chlorine, bromine or        iodine atom and n represents an integer of 0 to 20),    -   XCH₂CO₂—(CH₂) _(n)—OCOCH₂X, CH₃C(H) (X)CO₂—(CH₂) _(n)—OCOC(H)        (X)CH₃, (CH₃) ₂C(X)CO₂—(CH₂) _(n)—OCOC(X) (CH₃) ₂    -    (in the above formulas, n represents an integer of 1 to 20),    -   XCH₂C(O)C(O)CH₂X, CH₃C(H) (X)C(O)C(O)C(H) (X) CH₃, (CH₃)        ₂C(X)C(O)C(O)C(X) (CH₃) ₂, o-, m- or p-XCH₂CO₂—C₆H₄—OCOCH₂X, o-,        m- or p-CH₃C(H) (X)CO₂—C₆H₄—OCOC(H) (X)CH₃, o-, m- or p-(CH₃)        ₂C(X)CO₂—C₆H₄—OCOC(X) (CH₃) ₂, o-, m- or p-XSO₂—C₆H₄—SO₂X    -    (in the above formulas, X represents a chlorine, bromine or        iodine atom).

The transition metal complex to be used as the polymerization catalystis not particularly restricted but includes, as preferred species,transition metal complexes the central metal of which belongs to thegroup 7, 8, 9, 10 or 11 of the periodic table of the elements. As morepreferred species, there may be mentioned complexes of zero-valencecopper, univalent copper, bivalent ruthenium, bivalent iron or bivalentnickel. Copper complexes are preferred among others. As specificexamples of the univalent copper compound, there may be mentionedcuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide,cuprous oxide and cuprous perchlorate. When a copper compound is used, aligand, for example 2,2′-bipyridyl or a derivative thereof,1,10-phenanthroline or a derivative thereof, or a polyamine such astetramethylethylenediamine, pentamethyldiethylenetriamine orhexamethyltris(2-aminoethyl) amine, is added for increasing thecatalytic activity. The tristriphenylphosphine complex of bivalentruthenium chloride (RuCl₂(PPh₃)₃) is also suited for use as thecatalyst. When a ruthenium compound is used as the catalyst, an aluminumalkoxide is added as an activator. Further, the bistriphenylphosphinecomplex of bivalent iron (FeCl₂(PPh₃)₂), the bistriphenylphosphinecomplex of bivalent nickel (NiCl₂(PPh₃) ₂) and the bistributylphosphinecomplex of bivalent nickel (NiBr₂(PBu₃) ₂) are also suited as catalysts.

The vinyl monomer to be used in this polymerization is not particularlyrestricted but any of those already mentioned specifically hereinabovecan appropriately be used.

The above polymerization reaction can be carried out without using anysolvent or in any of various organic solvents. As the solvents, theremay be mentioned hydrocarbon solvents such as benzene and toluene; ethersolvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisoleand dimethoxybenzene; halogenated hydrocarbon solvents such as methylenechloride, chloroform and chlorobenzene; ketone solvents such as acetone,methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such asmethanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butylalcohol; nitrile solvents such as acetonitrile, propionitrile andbenzonitrile; ester solvents such as ethyl acetate and butyl acetate;carbonate solvents such as ethylene carbonate and propylene carbonate;and so on. These may be used singly or two or more of them may be usedin admixture. It is also possible to carry out the polymerization in anemulsion system or a system in which the supercritical fluid CO₂ is usedas a medium.

This polymerization can be carried out in the temperature range of 0 to200° C., preferably within the range of room temperature to 150° C.,although such range is not critical.

<General Schema for Introduction of a Terminal Functional Group forPolymer (I)>

The method for introduction of a terminal functional group for polymer[I] is now described in detail.

In the present invention, the technology of introducing a group of thegeneral formula (1) into the polymer terminus is not particularlyrestricted but includes the following processes.

-   -   {circle over (1)} The process which comprises substituting a        compound of the following general formula (2) for a terminal        halogen group of a vinyl polymer having a halogen atom at a        molecular chain terminus.        M⁺⁻OC(O)CR¹═CR²R³   (2)    -    [wherein R¹, R² and R³ are as defined hereinbefore; M⁺        represents an alkali metal ion or a quaternary ammonium ion]    -   {circle over (2)} The process which comprises reacting a vinyl        polymer having a hydroxyl group at a molecular chain terminus        with a compound of the general formula (4).        XC(O)CR¹═CR²R³   (4)    -    [wherein R, R² and R³ are as defined hereinbefore; X represents        a chlorine or bromine atom or a hydroxyl group]    -   {circle over (3)} The process which comprises reacting a vinyl        polymer having a hydroxyl group at a molecular chain terminus        with a diisocyanate compound and causing the residual unreacted        isocyanato group to react with a compound of the general formula        (5).        HO-Q-C(O)CR¹═CR²R³   (5)    -    [wherein R¹, R²and R³are as defined hereinbefore; Q represents        a bivalent organic group containing 2 to 20 carbon atoms]    -   {circle over (4)} The process which comprises reacting a vinyl        polymer (II) having a silanol group at at least one molecular        chain terminus with a silicon compound of the general formula        (6).        X′SiR″₂-G-C(O)CR¹═CR²R³   (6)    -    [wherein R¹, R² and R³ are as defined hereinbefore; R″        represents a hydrocarbon group containing 1 to 14 carbon atoms        or a halogenated hydrocarbon group containing 1 to 10 carbon        atoms; the plurality of R″ may be the same or different; X′        represents a hydrolyzable group; G represents an oxyalkylene        group of 1 to 4 carbon atoms]

In this specification, the vinyl polymer (II) having a silanol group atat least one molecular chain terminus is sometimes referred to brieflyas polymer (II).

The above processes are respectively described in detail below.

<Introduction {circle over (1)} of a Terminal Functional Group forPolymer (I)>

The process {circle over (1)} is now described in detail.

-   -   {circle over (1)} The process which comprises substituting a        compound of the following general formula (2) for a terminal        halogen group of a vinyl polymer having a halogen atom at a        molecular chain terminus.        M⁺⁻OC(O) CR¹═CR²R³   (2)    -   (wherein R¹, R²and R³are as defined hereinbefore; M⁺ represents        an alkali metal ion or a quaternary ammonium ion)

The halogen-containing terminus of the vinyl polymer having a halogenatom at a molecular chain terminus is preferably the structurerepresented by the following general formula (3):—CR²²R²³X  (3)

-   -   [wherein R²² and R²³ each represents a group linked to the        ethylenically unsaturated group of the vinyl monomer; X        represents a chlorine, bromine or iodine group]

The vinyl polymer having a terminal structure of the general formula (3)can be produced by the above-mentioned method for polymerizing a vinylmonomer using an organohalogen compound or a sulfonyl halide compound asthe initiator and a transition metal complex as the catalyst or theabove-mentioned method for polymerizing a vinyl monomer using a halogencompound as the chain transfer agent, preferably by the former method.

Referring to the above general formula (2), M⁺ represents the countercation to the oxyanion, for example, an alkali metal ion or a quaternaryammonium ion. As specific examples of the alkali metal ion, there may bementioned the lithium ion, sodium ion and potassium ion. As thequaternary ammonium ion, there may be mentioned the tetramethylammoniumion, tetraethylammonium ion, tetrabenzylammonium ion,trimethyldodecylammonium ion, tetrabutylammonium ion anddimethylpiperidinium ion. Preferred are sodium ion and potassium ion.

The amount of use of the oxyanion of the general formula (2) ispreferably 1 to 5 equivalents, more preferably 1.0 to 1.2 equivalentsrelative to a terminal halogen group of the general formula (3). Thesolvent for use in carrying out this reaction is not particularlyrestricted but, because the reaction is a nucleophilic substitutionreaction, is preferably a polar solvent such as, for example,tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide,dimethylformamide, dimethylacetamide, hexamethylphosphoric amide,acetonitrile and so on. The reaction temperature is not particularlyrestricted but generally the reaction is conducted at 0 to 150° C.,preferably at a temperature not over 100° C. for sustaining thepolymeric terminal group, more preferably at room temperature.

<Introduction {circle over (2)} of a Terminal Functional Group forPolymer (I)>

The process {circle over (2)} mentioned above is described.

{circle over (2)} The process which comprises reacting a vinyl polymerhaving a hydroxyl group at a molecular chain terminus with a compound ofthe general formula (4).XC(O)CR¹═CR²R³   (4)

-   -   wherein R¹, R²and R³are as defined hereinbefore; X represents a        chlorine or bromine atom or a hydroxyl group.

The vinyl polymer having a hydroxyl group at a molecular chain terminuscan be produced by the above-mentioned method for polymerizing a vinylmonomer using an organohalogen compound or a sulfonyl halide compound asthe initiator and a transition metal complex as the catalyst or theabove-mentioned method for polymerizing a vinyl monomer using a hydroxylgroup-containing compound as the chain transfer agent, preferably by theformer method. The specific technique which can be used for producing avinyl polymer having a hydroxyl group at a molecular chain terminus isnot restricted but includes the following processes in addition to theabove-mentioned method using a hydroxyl group-containing initiator.

-   (a) The process which comprises subjecting a compound having both a    polymerizable alkenyl group and a hydroxyl group as represented by    the following general formula (12) to reaction as a second monomer    in synthesizing the vinyl polymer by living radical polymerization:    H₂C═C(R¹⁵)-R¹⁶-R¹⁷—OH  (12)    -   wherein R¹⁵ represents an organic group containing 1 to 20        carbon atoms, preferably a hydrogen atom or a methyl group, and        may be the same or different; R¹⁶ represents —C(O)O— (an ester        group) or an o-, m- or p-phenylene group; R¹⁷ represents a        direct bond or a bivalent organic group containing 1 to 20        carbon atoms which may optionally contain one or more ether        linkages. The compound in which R¹⁵ represents an ester group is        a (meth)acrylate compound and the compound in which R¹⁶        represents a phenylene group is a styrenic compound.

The timing of reacting the compound having both a polymerizable alkenylgroup and a hydroxyl group in each molecule is not particularlyrestricted but, when the expression of rubber-like propertiesareexpected, the compound is subjected to reaction as a second monomerpreferably at the final stage of the polymerization reaction or aftercompletion of the reaction of the predetermined vinyl monomer.

-   (b) The process which comprises subjecting a compound having a    sparingly polymerizable alkenyl group and a hydroxyl group in each    molecule to reaction as a second monomer at the final stage of the    polymerization reaction or after completion of the reaction of the    predetermined vinyl monomer in synthesizing the vinyl polymer by    living radical polymerization. Such compound is not particularly    restricted but includes, among others, compounds represented by the    general formula (13):    H₂C═C(R¹⁵)-R¹⁸—OH  (13)    -   wherein R¹⁵ is as defined above and R¹⁸ represents a bivalent        C₁₋₂₀ organic group optionally containing one or more ether        linkages.

The compound represented by the above general formula (13) is notparticularly restricted but alkenyl alcohols such as 10-undecenol,5-hexenol and allyl alcohol are preferred from availability points ofview.

-   (c) The process disclosed in Japanese Kokai Publication    Hei-04-132706, for instance, which comprises terminally introducing    a hydroxyl group by hydrolyzing the halogen of a vinyl polymer    having at least one carbon-halogen bond represented by the general    formula (2) as obtained by atom transfer radical polymerization or    reacting the halogen with a hydroxyl-containing compound.-   (d) The process which comprises reacting a vinyl polymer having at    least one carbon-halogen bond represented by the general formula (3)    as obtained by atom transfer radical polymerization with a    stabilized, hydroxyl-containing carbanion such as one represented by    the general formula (14) to thereby effect substitution for the    halogen:    M⁺C⁻(R²³) (R²⁴)-R¹⁸—OH  (14)    -   wherein R¹⁸ is as defined above; R²³ and R²⁴ each represents an        electron-attracting group stabilizing the carbanion C⁻ or one of        them represents such an electron-attracting group and the other        represents a hydrogen atom, an alkyl group containing 1˜10        carbon atoms or a phenyl group. As the electron-attracting group        R²³ and/or R²⁴, there may be mentioned —CO₂R (ester group)        —C(O)R (keto group), —CON(R₂) (amide group), —COSR (thioester        group), —CN (nitrile group) and —NO₂ (nitro group), among        others. The substituent R is an alkyl group containing 1 to 20        carbon atoms, an aryl group containing 6 to 20 carbon atoms or        an aralkyl group containing 7 to 20 carbon atoms and preferably        is an alkyl group containing 1 to 10 carbon atoms or a phenyl        group. Particularly preferred as R²³ and R²⁴ are —CO₂R, —C(O)R        and —CN.-   (e) The process which comprises reacting a vinyl polymer having at    least one carbon-halogen bond represented by the general formula (3)    as obtained by atom transfer radical polymerization with a simple    substance metal, such as zinc, or an organometal compound and then    reacting the thus-prepared enolate anion with an aldehyde or ketone.-   (f) The process which comprises reacting a vinyl polymer having at    least one terminal halogen, preferably a halogen represented by the    general formula (3), with a hydroxyl-containing oxyanion represented    by the general formula (15) shown below or the like or a    hydroxyl-containing carboxylate anion represented by the general    formula (16) shown below or the like to thereby substitute a    hydroxyl-containing substituent for the above halogen:    HO—R¹⁸—O⁻M⁺  (15)    -   wherein R¹⁸ and M⁺ are as defined above;        HO—R¹⁸—C(O)O⁻M⁺  (16)    -   wherein R¹⁸ and M⁺ are as defined above.

In the practice of the invention, when any halogen is not directlyinvolved in the method comprising introducing a hydroxyl group, as inthe processes (a) and (b), the process (b) is comparatively morepreferred since the control is easier. In cases where the hydroxyl groupintroduction is introduced by converting the halogen of a vinyl polymerhaving at least one carbon-halogen bond, as in the processes (c) to (f),the process (f) is comparatively more preferred since the control iseasier.

<Introduction {circle over (3)} of a Terminal Hydroxyl Group for Polymer(I)>

The process {circle over (3)} is now described.

-   {circle over (3)} The process which comprises reacting a vinyl    polymer having a hydroxyl group at a molecular chain terminus with a    diisocyanate compound and causing the residual unreacted isocyanato    group to react with a compound of the general formula (5).    HO-Q-C(O)CR¹═CR²R³   (5)    -   [wherein R¹, R² and R³ are as defined hereinbefore; Q represents        a bivalent organic group containing 2 to 20 carbon atoms]

Referring to the above general formula (5), Q includes but is notlimited to:

-   —(CH₂)_(n)— (n being an integer of 1 to 20); —CH(CH₃)—,    —CH(CH₂CH₃)—, —C(CH₃)₂—, —C(CH₃) (CH₂CH₃)—, —C(CH₂CH₃)₂—,    —CH₂CH(CH₃)—; —(CH₂)_(n)—O— (n being an integer of 1 to 20);    —CH(CH₃)—O—, —CH(CH₂CH₃)—O—, —C(CH₃) ₂—O—, —C(CH₃) (CH₂CH₃)—O—,    —C(CH₂CH₃) ₂—O—; —(CH₂) _(n)—O—CH₂— (n being an integer of 1 to 19);    —CH(CH₃)—O—CH₂—, —CH(CH₂CH₃)—O—CH₂—, —C(CH₃) ₂—O—CH₂—O—C(CH₃)    (CH₂CH₃)—O—CH₂—, —C(CH₂CH₃) ₂—O—CH₂—, —(CH₂) _(n)—OC(O)—; —(CH₂)    _(n)—OC(O)—(CH₂)_(m)— (m and n being the same or different and each    being an integer of 0 to 19, provided that the relation 0≦m+n≦19    should be satisfied);-   —(CH₂)_(n)—C(O)O—(CH₂)_(m)— (m and n being the same or different and    each being an integer of 0 to 19, provided that the relation    0≦m+n≦19 should be satisfied); —CH₂—C(O)O—(CH₂)₂—O—CH₂—, —CH (CH₃)    —C(O)O—(CH₂) ₂—O—CH₂—, —CH(CH₂CH₃) —C(O)O—(CH₂)₂—O—, —C(CH₃)    ₂—C(O)O—, —C(CH₃) (CH₂CH₃)—C(O)O—, —C(CH₂CH₃)₂—C(O)O— and the like.

Further Q may contain a benzene ring. As specific examples of that case,there may be mentioned o-, m- or p-C₆H₄—, o-, m- or p-C₆H₄—CH₂—, o-, m-or p-C₆H₄—O—, o-, m- or p-C₆H₄—, O—CH₂—, o-, m- or p-C₆H₄—O—CH(CH₃)—,o-, m- or p-C₆H₄—O—C(CH₃)₂—; o-, m- or p-C₆H₄—(CH₂)— (n being an integerof 0 to 14); o-, m- or p-C₆H₄—O—(CH₂)_(n)— (n being an integer of 0 to14); o-, m- or p-CH₂—C₆H₄—, o-, m- or p-CH₂—C₆H₄—CH₂—, o-, m- orp-CH₂—C₆H₄—O—, o-, m- or p-CH₂—C₆H₄—O—CH₂—, o-, m- orp-CH₂—C₆H₄—O—CH(CH₃)—; o-, m- or p-CH₂—C₆H₄—O—C(CH₃) ₂—; o-, m- orp-CH₂—C₆H₄—(CH₂) _(n)— (n being an integer of 0 to 13); o-, m- orp-CH₂—C₆H₄—O—(CH₂)_(n)— (n being an integer of 0 to 13); o-, m- orp-C₆H₄—C(O)O—, o-, m- or p-CH₂—C₆H₄—C(O)O—; o-, m- orp-C(O)—C₆H₄—C(O)O—(CH₂) _(n)— (n being an integer of 0 to 12) and thelike.

The hydroxyl-terminated vinyl monomer is as described above.

The diisocyanate compound for use is not particularly restricted and maybe any of the hitherto-known isocyanates, such as toluylenediisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethyldiisocyanate, xylylene diisocyanate, m-xylylene diisocyanate,1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate,isophorone diisocyanate, and so on. These may be used each independentlyor two or more of them may be used in combination. Blocked isocyanatesmay also be used.

As the polyisocyanate for insuring more improved weather resistance, itis preferable to use a aromatic ring-free diisocyanate compound such ashexamethylene diisocyanate and hydrogenated diphenylmethanediisocyanate.

<Introduction {circle over (4)} of a Terminal Functional Group forPolymer (I)>

The process {circle over (4)} is now described.

-   {circle over (4)} The process which comprises reacting a vinyl    polymer (II) having a silanol group at at least one molecular chain    terminus with a silicon compound of the general formula (6).    X′SiR″₂-G-C(O)CR¹═CR²R³   (6)    -   [wherein R¹, R²and R³ are as defined hereinbefore; R¹⁰        represents a hydrocarbon group containing 1 to 14 carbon atoms        or a halogenated hydrocarbon group containing 1 to 10 carbon        atoms; the plurality of R″ may be the same or different; X′        represents a hydrolyzable group; G represents an oxyalkylene        group containing 1 to 4 carbon atoms]

The vinyl polymer (II) having a silanol group at at least one terminus[hereinafter sometimes referred to briefly as polymer (II)] is nowdescribed.

The silanol group of polymer (II) is not restricted but includes groupswhich may be represented by the general formula (7).—[Si(R⁵) _(2-b)(OH) _(b)O]_(m)—Si (R⁶) _(3-a)(OH)_(a)  (7)

-   -   [wherein R⁵ and R⁶ each represents an alkyl group containing 1        to 20 carbon atoms, an aryl group containing 6 to 20 carbon        atoms, an aralkyl group containing 7 to 20 carbon atoms, or a        triorganosiloxy group of the formula (R′)₃Si— (where R′        represents a univalent hydrocarbon group containing 1 to 20        carbon atoms and the three R′ groups may be the same or        different); when R⁵ or R⁶ occurs in the number of 2 or more, the        plurality of groups may be the same or different; a represents        0, 1, 2 or 3; b represents 0, 1 or 2; m is an integer of 0 to        19; provide, however, that the relation of a+mb≧1 is satisfied]

Though this is not an exclusive choice, the silanol group of the generalformula (7) wherein m=0 is preferred.

R⁵ and R⁶ include but are not limited to the following groups:

-   —(CH₂) _(n)—CH₃, —CH(CH₃)—(CH₂) _(n)—CH₃, —CH(CH₂CH₃)—(CH₂)    _(n)—CH₃, —CH(CH₂CH₃)₂, —C(CH₃)₂—(CH₂) _(n)—CH₃, —C (CH₃)    (CH₂CH₃)—(CH₂) _(n)—CH₃, —C₆H₅—, —C₆H₅(CH₃), —C₆H₅(CH₃) ₂, —(CH₂)    _(n)—C₆H₅, —(CH₂) _(n)—C₆H₅(CH₃), —(CH₂) _(n)—C₆H₅(CH₃) ₂    -   (n is an integer of 0 or more; the total number of carbon atoms        in each group is up to 20 at the maximum)

More specifically, the preferred silanol group of polymer (II) is—Si(CH₃)₂OH.

A typical technology of producing a vinyl polymer (II) having a silanolgroup at at least one terminus is now described below. However, this isnot limited thereto. For information on suitable processes forsynthesizing a silanol-containing polymer, reference may be made to P.D. Lickiss' article in Advances in Inorganic Chemistry, Vol. 42, p. 142(1995).

The basic method of producing said polymer (II) comprises polymerizing avinyl monomer, introducing an alkenyl group into the terminus of thepolymer in some way or other, subjecting it to hydrosilylation with asilicon compound having both a hydrolyzable group and a hydrosilylgroup, hydrolyzing said hydrolyzable group for conversion to a silanolgroup.

This method is now described in detail. Alkenyl group introduction Themethod of producing a vinyl polymer having at least one alkenyl group ata terminus is not limited to the above method using analkenyl-containing initiator but includes the following methods (A) to(C), for instance.

-   (A) The method comprising directly introducing an alkenyl group into    the polymer main chain on the occasion of synthesizing a vinyl    polymer by radical polymerization.-   (B) The method comprising using a vinyl polymer having at least one    halogen and substituting an alkenyl-containing functional group for    this halogen. The halogen group is not restricted but is preferably    represented by the general formula (3):    —C(R²²) (R²³) (X)  (3)    -   wherein R²² and R²³ each represents a group bound to an        ethylenically unsaturated group of the vinyl monomer and X        represents a chlorine, bromine or iodine atom.-   (C) The method comprising using a vinyl polymer having at least one    hydroxyl group and substituting an alkenyl-containing functional    group for this hydroxyl group.

Referring to the above method of synthesis (A), the process for directlyintroducing an alkenyl group into the polymer main chain is notparticularly restricted but specifically includes, among others, theprocesses (A-a) and (A-b) mentioned below.

(A-a) The process which comprises subjecting a compound having both apolymerizable alkenyl group and a sparingly polymerizable alkenyl groupper molecule as represented by the following general formula (17) toreaction together with a predetermined vinyl monomer on the occasion ofsynthesizing a vinyl polymer by living radical polymerization:H₂C═C(R¹⁵)-R¹⁶-R¹⁷—C(R¹⁵)═CH₂   (17)

-   -   wherein R¹⁵ is as defined above, R¹⁶ represents a —C(O)O—        (ester) group or an o-, m- or p-phenylene group, R¹⁷ represents        a direct bond or a bivalent C₁₋₂₀ organic group optionally        containing one or more ether bonds. When R¹⁶ is an ester group,        the compound is a (meth) acrylate compound and, when R¹⁶ is a        phenylene group, the compound is a styrenic compound.

As examples of R¹⁷ in the above general formula (17), there may bementioned alkylene groups such as methylene, ethylene and propylene; o-,m- and p-phenylene; aralkyl groups such as benzyl; and etherbond-containing alkylene groups such as —CH₂CH₂—O—CH₂— and —O—CH₂—.

Among the compounds of the general formula (17), the following arepreferred because of ready availability:

-   -   H₂C═C(H)C(O)O(CH₂)_(n)—CH═CH₂, H₂C═C(CH₃)C(O)O(CH₂) _(n)—CH═CH₂    -    (in the above formulas, n represents an integer of 0 to 20),    -   H₂C═C(H)C(O)O(CH₂) _(n)—O—(CH₂) _(m)CH═CH₂, H₂C═C(CH₃)C(O)O(CH₂)        _(n)—O—(CH₂) _(m)CH═CH₂    -    (in the above formulas, n represents an integer of 1 to 20 and        m represents an integer of 0 to 20),    -   o-, m-, p-divinylbenzene, o-, m-, p-H₂C═CH—C₆H₄—CH₂CH═CH₂, o, m,        p-H₂C═CH—C₆H₄—CH₂—C(CH₃)═CH₂, o, m, p-H₂C═CH—C₆H₄—CH₂CH₂CH═CH₂,        o, m, p-H₂C═CH—C₆H₄—OCH₂CH═CH₂, o, m,        p-H₂C═CH—C₆H₄—OCH₂—C(CH₃)═CH₂, o, m,        p-H₂C═CH—C₆H₄—OCH₂CH₂CH═CH₂, o, m, p-H₂C═C(CH₃)—C₆H₄—C(CH₃)═CH₂,        o, m, p-H₂C═C(CH₃)—C₆H₄—CH₂CH═CH₂, o, m, p-H₂C═C        (CH₃)—C₆H₄—CH₂C(CH₃)═CH₂, o, m, p-H₂C═C(CH₃)—C₆H₄—CH₂CH₂CH═CH₂,        o, m, p-H₂C═C(CH₃)—C₆H₄—OCH₂CH═CH₂, o, m, p-H₂C═C        (CH₃)—C₆H₄—OCH₂—C(CH₃)═CH₂, and o, m,        p-H₂C═C(CH₃)—C₆H₄—OCH₂CH₂CH═CH₂    -    (in the above formulas, C₆H₄ represents a phenylene group)

The timing of reacting the compound having both a polymerizable alkenylcompound and a sparingly polymerizable alkenyl group is not particularlyrestricted. Preferably, however, it is subjected to reaction as a secondmonomer at the final stage of the polymerization reaction or aftercompletion of the reaction involving a predetermined monomer(s) in theliving radical polymerization.

-   (A-b) The process which comprises subjecting a compound having at    least two sparingly polymerizable alkenyl groups to reaction as a    second monomer at the final stage of the polymerization reaction or    after completion of the reaction involving a predetermined    monomer(s) in synthesizing a vinyl polymer by living radical    polymerization.

Such compound is not particularly restricted but includes, among others,compounds represented by the general formula (18):H₂C═C(R¹⁵)-R¹⁸—C(R¹⁵)═CH₂   (18)

-   -   wherein R¹⁵ is as defined above, R¹⁸ represents a bivalent        organic group containing 1 to 20 carbon atoms, which may        optionally contain one or more ether bonds.

The compound represented by the above general formula (18) is notparticularly restricted. Preferred are, however, 1,5-hexadiene,1,7-octadiene and 1,9-decadiene in view of their ready availability.

Among the variations of the above synthetic method (A) for synthesizinga vinyl polymer having at least one alkenyl group which comprisesdirectly introducing the alkenyl group into the polymer main chain, themethod (A-b) is preferred since the number of alkenyl groups introducedper polymer molecule can be controlled more easily.

The above method (B) for synthesizing a vinyl polymer having at leastone halogen atom, preferably the halogen atom represented by the generalformula (3) at the polymer terminus is preferably carried out in themanner of atom transfer living polymerization. The method ofsubstituting an alkenyl-containing functional group for the halogen atomof that polymer is not particularly restricted but specificallyincludes, among others, the processes (B-a) to (B-d) described below.

-   (B-a) The process which comprises reacting a vinyl polymer having at    least one halogen atom, preferably a halogen atom represented by the    general formula (3) at the polymer terminus with one of various    alkenyl-containing organometal compounds to thereby substitute the    alkenyl for the halogen.

As such organometal compounds, there may be mentioned organolithium,organosodium, organopotassium, organomagnesium, organotin,organosilicon, organozinc, organocopper and like compounds. Inparticular, roganotin and organocopper compounds are preferred sincethey react selectively with the halogen represented by the generalformula (3) and are low in reactivity with a carbonyl group.

The alkenyl-containing organotin compound is not particularly restrictedbut compounds represented by the general formula (19):H₂C═C(R¹⁵)C(R¹⁹) (R²⁰)Sn(R²¹)₃   (19)

-   -   wherein R¹⁵ is as defined above, R¹⁹ and R²⁰ each represents a        hydrogen atom, an alkyl group containing 1 to 10 carbon atoms,        an aryl group containing 6 to 10 carbon atoms or an aralkyl        group containing 7 to 10 carbon atoms and they may be the same        or different, R²¹ represents a C₁-C₁₀ alkyl, aryl or aralkyl        group.

As specific examples of the organotin compound of the above generalformula (19), there may be mentioned allyltributyltin,allyltrimethyltin, allyltri(n-octyl)tin and allyltri(cyclohexyl)tin. Asexamples of the alkenyl-containing organocopper compound, there may bementioned divinylcopper-lithium, diallylcopper-lithium anddiisopropenylcopper-lithium.

-   (B-b) The process which comprises reacting a vinyl polymer having at    least one halogen atom, preferably a halogen atom represented by the    general formula (3) at the polymer terminus, with a stabilized    alkenyl-containing carbanion represented by the following general    formula (20), for instance, to thereby substitute the alkenyl for    the halogen:    M⁺C⁻(R²³)(R²⁴)-R¹⁸—C(R¹⁵)═CH₂   (20)    -   wherein R¹⁵ and R¹⁸ are as defined above. R²³ and R²⁴ each        represents an electron-attracting group stabilizing the        carbanion C⁻ or one of them represents such an        electron-attracting group and the other represents a hydrogen        atom, an alkyl group containing 1 to 10 carbon atoms or a phenyl        group. As the electron-attracting group R²³ and/or R²⁴, there        may be mentioned —CO₂R (ester group), —C(O)R (keto group),        —CON(R₂) (amide group), —COSR (thioester group), —CN (nitrile        group) and —NO₂ (nitro group), among others. The substituent R        is an alkyl group containing 1 to 20 carbon atoms, an aryl group        containing 6 to 20 carbon atoms or an aralkyl group containing 7        to 20 carbon atoms and preferably is an alkyl group containing 1        to 10 carbon atoms or a phenyl group. Particularly preferred as        R²³ and R²⁴ are —CO₂R, —C(O)R and —CN. M⁺ represents an alkali        metal ion or a quaternary ammonium ion.

As the alkali metal ion, there may be mentioned the lithium ion, sodiumion and potassium ion and, as the quaternary ammonium ion, there may bementioned the tetramethylammonium ion, tetraethylammonium ion,trimethylbenzylammonium ion, trimethyldodecylammonium ion andtetrabutylammonium ion.

The carbanion of the general formula (20) can be obtained by reacting aprecursor thereof with a basic compound to thereby withdraw the activeproton.

As examples of the precursor of the carbanion of the general formula(20), there may be mentioned the following compounds:

-   -   H₂C═CH—CH(CO₂CH₃)₂, H₂C═CH—CH(CO₂C₂H₅)₂, H₂C═CH—(CH₂)        _(n)CH(CO₂CH₃)₂, H₂C═CH— (CH₂) _(n)CH (CO₂C₂H₅) ₂, o-, m-,        p-H₂C═CH—C₆H₄—CH(CO₂CH₃) ₂, o-, m-, p-H₂C═CH—C₆H₄—CH(CO₂C₂H₅) ₂,        o-, m-, p-H₂C═CH—C₆H₄—CH₂CH(CO₂CH₃) ₂, o-, m-,        p-H₂C═CH—C₆H₄—CH₂CH(CO₂C₂H₅) ₂, H₂C═CH—CH(C(O)CH₃) (CO₂C₂H₅),        H₂C═CH—(CH₂)_(n)CH(C(O)CH₃) (CO₂C₂H₅), o-, m-,        p-H₂C═CH—C₆H₄—CH(C(O)CH₃) (CO₂C₂H₅), o-, m-, p-H₂C═CH—C₆H₄—CH₂CH        (C(O)CH₃) (CO₂C₂H₅), H₂C═CH—CH(C(O)CH₃)₂, H₂C═CH—(CH₂)        _(n)CH(C(O)CH₃) ₂, o-, m-, p-H₂C═CH—C₆H₄—CH(C(O)CH₃)₂, o-, m-,        p-H₂C═CH—C₆H₄—CH₂CH(C(O)CH₃) ₂, H₂C═CH—CH(CN) (CO₂C₂H₅),        H₂C═CH—(CH₂)_(n)CH (CN) (CO₂C₂H₅), o-, m-, p-H₂C═CH—C₆H₄—CH(CN)        (CO₂C₂H₅), o-, m-, p-H₂C═CH—C₆H₄—CH₂CH(CN) (CO₂C₂H₅),        H₂C═CH—CH(CN)₂, H₂C═CH—(CH₂)_(n)CH(CN), o-, m-,        p-H₂C═CH—C₆H₄—CH(CN)₂, o-, m-, p-H₂C═CH—C₆H₄—CH₂CH(CN)₂,        H₂C═CH—(CH₂)_(n)NO₂, o-, m-, p-H₂C═CH—C₆H₄—CH₂NO₂, o-, m-,        p-H₂C═CH—C₆H₄—CH₂CH₂NO₂, H₂C═CH—CH(C₆H₅) (CO₂C₂H₅),        H₂C═CH—(CH₂)_(n)CH(C₆H₅)(CO₂C₂H₅), o-, m-,        p-H₂C═CH—C₆H₄—CH(C₆H₅)(CO₂C₂H₅), o-, m-,        p-H₂C═CH—C₆H₄—CH₂CH(C₆H₅) (CO₂C₂H₅)    -    (in the above formulas, n represents an integer of 1 to 10).

For withdrawing a proton from the above compound to give the carbanionof the general formula (20) , various basic compounds are usable. Assuch basic compounds, there may be mentioned the following:

Alkali metals such as sodium, potassium and lithium; metal alkoxidessuch as sodium methoxide, potassium methoxide, lithium methoxide, sodiumethoxide, potassium ethoxide, lithium ethoxide, sodium tert-butoxide andpotassium tert-butoxide; carbonates such as sodium carbonate, potassiumcarbonate, lithium carbonate and sodium hydrogen carbonate; hydroxidessuch as sodium hydroxide and potassium hydroxide; hydrides such assodium hydride, potassium hydride, methyllithium and ethyllithium;organometals such as n-butyllithium, tert-butyllithium, lithiumdiisopropylamide and lithium hexamethyldisilazide; ammonia; alkylaminessuch as trimethylamine, triethylamine and tributylamine; polyamines suchas tetramethylethylenediamine and pentamethyl-diethylenetriamine; andpyridine compounds such as pyridine and picoline; among others.

The basic compound is used in an equivalent amount or in a slight excessrelative to the precursor substance, preferably in an amount of 1 to 1.2equivalents.

A quaternary ammonium salt may also be used as the above carbanion. Inthis case, it can be obtained by preparing an alkali metal salt of acarboxylic acid compound and reacting this with a quaternary ammoniumhalide. As examples of the quaternary ammonium halide, there may bementioned tetramethylammonium halides, tetraethylammonium halides,trimethylbenzylammonium halides, trimethyldodecylammonium halides andtetrabutylammonium halides.

As the solvent to be used in reacting the above precursor with a basiccompound, there may be mentioned hydrocarbon solvents such as benzeneand toluene; ether solvents such as diethyl ether, tetrahydrofuran,diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbonsolvents such as methylene chloride and chloroform; ketone solvents suchas acetone, methyl ethyl ketone and methyl isobutyl ketone; alcoholsolvents such as methanol, ethanol, propanol, isopropanol, n-butylalcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile,propionitrile and benzonitrile; ester solvents such as ethyl acetate andbutyl acetate; carbonate solvents such as ethylene carbonate andpropylene carbonate; amide solvents such as dimethylformamide anddimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; and soon. These may be used singly or two or more of them may be used inadmixture.

By reacting the above precursor with a basic compound, a carbanionrepresented by the general formula (20) is prepared and, by reacting thesame with a vinyl polymer having a terminal halogen atom, preferably ahalogen represented by the general formula (3), the desiredalkenyl-terminated vinyl polymer can be obtained.

-   (B-c) The process which comprises reacting a vinyl polymer having at    least one halogen atom, preferably a halogen atom represented by the    general formula (3) at the polymer terminus with a simple substance    metal or an organometal compound to thereby form an enolate anion    and then reacting it with an alkenyl-containing electrophilic    compound.

Particularly preferred as the simple substance metal is zinc, since theresulting enolate anion will not attack other ester groups or hardlyundergo such side reactions as rearrangement. Various species can beused as the alkenyl-containing electrophilic compound, for examplealkenyl-containing compounds having a leaving group such as a halogenand an acetyl group, alkenyl-containing carbonyl compounds,alkenyl-containing isocyanate compounds and alkenyl-containing acidhalides. Among these, alkenyl-containing compounds having a leavinggroup such as a halogen and an acetyl group are preferred since whenthey are used, no other atoms than carbon atoms are introduced into themain chain, hence the vinyl polymer will not lose its weatheringresistance.

-   (B-d) The process comprising reacting a vinyl polymer having at    least one halogen atom, preferably a halogen represented by the    general formula (3) at the polymer terminus, with an    alkenyl-containing oxyanion represented by the general formula (21)    given below or an alkenyl-containing carboxylate anion represented    by the general formula (22) given below to thereby substitute the    alkenyl group for the above halogen:    CH₂═C(R) -R¹⁸—O⁻M⁺  (21)    -   wherein R¹⁵, R¹⁸ and M⁺ are as defined above;        CH₂═C(R¹⁵)-R¹⁸—C(O)O⁻M⁺  (22)    -   wherein R¹⁵, R¹⁸ and M⁺ are as defined above.

As the precursor of the oxyanion represented by the general formula (21)or (22), there may be mentioned the following compounds:

Alcoholic hydroxyl-containing compounds such as H₂C═CH—CH₂—OH, H₂C═CH—CH(CH₃) —OH, H₂C═C(CH₃)—CH₂—OH, H₂C═CH—(CH₂)—OH (n being an integer of 2to 20) , H₂C═CH—CH₂—O—(CH₂) ₂—OH, H₂C═CH—C(O)O—(CH₂)₂—OH,H₂C═C(CH₃)—C(O)O—(CH₂)₂—OH, o-, m-, p-H₂C═CH—C₆H₄—CH₂—OH, o-, m-,p-H₂C═CH—CH₂—C₆H₄—CH₂—OH, o-, m-, p-H₂C═CH—CH₂—O—C₆H₄—CH₂—OH; phenolichydroxyl-containing compounds such as o-, m-, p-H₂C═CH—C₆H₄—OH, o-, m-,p-H₂C═CH—CH₂—C₆H₄—OH, o-, m-, p-H₂C═CH—CH₂—O—C₆H₄—OH;carboxyl-containing compounds such as H₂C═CH—C(O)—OH, H₂C═C(CH₃)—C(O)—OH, H₂C═CH—CH₂—C(O)—OH, H₂C═CH—(CH₂) _(n)—C(O)—OH (n being aninteger of 2 to 20), H₂C═CH—(CH₂)_(n)—OC(O)—(CH₂)_(m)—C(O)—OH (m and nbeing the same or different and each being an integer of 0 to 19), o-,m-, p-H₂C═CH—C₆H₄—C(O)—OH, o-, m-, p-H₂C═CH—CH₂—C₆H₄—C(O)—OH, o-, m-,p-H₂C═CH—CH₂—O—C₆H₄—C(O)—OH, o-, m-,p-H₂C═CH—(CH₂)_(n)—OC(O)—C₆H₄—C(O)—OH (n being an integer of 0 to 13);and the like.

For withdrawing a proton from the above compound to give an anion of thegeneral formula (21) or (22), one of various basic compounds is used. Asspecific examples thereof, those basic compounds which are mentionedhereinabove for use in preparing the carbanion of the general formula(20) are all suited for use. As for the reaction solvent, all thereaction solvents usable in preparing the carbanion can appropriately beused.

Among the variations of the synthetic method (B), since the alkenylgroup introduction can be realized at a high rate, preferred is themethod (B-d) which comprises being subjected a vinyl polymer at leastone halogen atom, preferably a halogen atom represented by the generalformula (3) at the polymer terminus, as obtained by atom transferradical polymerization using an organic halide or halogenated sulfonylcompound as an initiator and a transition metal complex as a catalyst,to halogen conversion. Among the variations of the method (B-d), themethod comprising reacting the polymer with an alkenyl-containingcarboxylate anion represented by the general formula 22 or the like ismore preferred.

When, in the process for producing a vinyl polymer which comprises usingthe atom transfer radical polymerization technique for polymerizing avinyl monomer(s) with an organic halide or halogenated sulfonyl compoundas an initiator and a transition metal complex as a catalyst, analkenyl-containing organic halide is used as the initiator, a vinylpolymer having the alkenyl group at one terminus and the halogen atom,preferably represented by the general formula (3), at the other terminuscan be obtained. When the termination terminus halogen of thethus-obtained polymer is converted to an alkenyl-containing substituent,a vinyl polymer having the respective alkenyl groups at the respectiveterminus can be obtained. As the method of conversion, the methodsalready described hereinabove can be used.

As the alkenyl-containing initiator, the compounds mentionedhereinbefore can be used with advantage.

The alkenyl-terminated vinyl polymer can also be produced by couplingthe halogen termini to each other using a compound having a total of 2or more functional groups, either the same or different, each of whichis capable of replacing the halogen of the polymer.

The compound having a total of at least two functional groups which arethe same or different and may substitute for the terminal halogen is notparticularly restricted but preferably includes polyols, polyamines,polycarboxylic acids, polythiols, and salts thereof, and alkali metalsulfides, among others. Specific examples of these compounds are asfollows:

Polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol,2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol,1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol,1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,1,12-dodecanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol,1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glycerol,1,2,4-butanetriol, catechol, resorcinol, hydroquinone,1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene,1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,2′-biphenol,4,4′-biphenol, bis(4-hydroxyphenyl) methane, 4,4′-isopropylidenephenol,3,3′-(ethylenedioxy) diphenol, α, α′-dihydroxy-p-xylene, 1,1,1-tris(4-hydroxyphenyl)ethane, pyrogallol and 1,2,4-benzenetriol; and alkalimetal salts of the polyol compounds mentioned above;

Polyamines such as ethylenediamine, 1,3-diaminopropane,1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-methylpropane,1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine,1,7-heptanediamine, 1,8-octanediamine, 1,9-diaminononane,1,10-diaminodecane, 1,12-diaminododecane,4,4′-methylenebis(cyclohexylamine), 1,2-diaminocyclohexane,1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-phenylenediamine,1,3-phenylenediamine, 1,4-phenylenediamine and α,α′-diamino-p-xylene;and alkali metal salts of the polyamine compounds mentioned above;

Polycarboxylic acids such as oxalic acid, malonic acid, methylmalonicacid, dimethylmalonic acid, succinic acid, methylsuccinic acid, glutaricacid, adipic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylicacid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid,1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid,1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid,1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,1,3,5-cyclohexanetricarboxylic acid, phthalic acid, isophthalic acid,terephthalic acid, 1,2,3-benzenetricarboxylic acid and1,2,4,5-benzenetetracarboxylic acid; and alkali metal salts of thepolycarboxylic acids mentioned above;

Polythiols such as 1,2-ethanedithiol, 1,3-propanedithiol,1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol,1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol,1,9-nonanedithiol, 2-mercaptoethyl ether, p-xylene-α, α′-dithiol,1,2-benzenedithiol, 1,3-benzenedithiol and 1,4-benzenedithiol; andalkali metal salts of the polythiols mentioned above;

Lithium sulfide, sodium sulfide and potassium sulfide.

When the above polyols, polyamines, polycarboxylic acids or polythiolsare used, a basic compound.is combinedly used for promoting thesubstitution reaction and, as specific examples, there may be mentionedthose already mentioned hereinabove.

The synthetic method (C) mentioned above which comprises using a.vinylpolymer having at least one hydroxyl group and substituting analkenyl-containing functional group for this hydroxyl group is notparticularly restricted but specifically includes, among others, theprocesses (C-a) to (C-d) mentioned below.

The vinyl polymer having at least one hydroxyl group can be obtained bythe processes described above.

-   (C-a) The process comprising reacting a hydroxyl group of a vinyl    polymer having at least one hydroxyl group with a base, such as    sodium hydroxide or sodium methoxide, followed by reacting with an    alkenyl-containing halide, such as allyl chloride.-   (C-b) The process comprising reacting a vinyl polymer having at    least one hydroxyl group with an alkenyl-containing isocyanate    compound, such as allyl isocyanate.-   (C-c) The process comprising reacting a vinyl polymer having at    least one hydroxyl group with an alkenyl-containing acid halide,    such as (meth)acrylic acid chloride, in the presence of a base, such    as pyridine.-   (C-d) The process comprising reacting a vinyl polymer having at    least one hydroxyl group with an alkenyl-containing carboxylic acid,    such as acrylic acid, in the presence of an acid catalyst.    Hydrosilylation Reaction

By subjecting the alkenyl-terminated polymer produced in the abovemanner to hydrosilylation reaction using a silicon compound having botha hydrolyzable group and a hydrosilyl group, the hydrosilyl group can beintroduced terminally into the polymer.

The silicon compound having both a hydrolyzable group and a hydrosilylgroup is not particularly restricted but includes compounds representedby the general formula (23):H—[Si(R⁵) _(2-b)(Y″) _(b)O]_(m)—Si(R⁶) _(3-a)(Y″) _(a)   (23)

-   -   wherein R⁵ and R⁶ each represents an alkyl group containing 1 to        20 carbon atoms, an aryl group containing 6 to 20 carbon atoms,        an aralkyl group containing 7 to 20 carbon atoms or a        triorganosiloxy group represented by (R′)₃SiO— (in which R′ is a        univalent hydrocarbon group containing 1 to 20 carbon atoms and        the three R′ groups may be the same or different) and, when        there are two or more R⁵ or R⁶ groups, they may be the same or        different, Y″ represents a hydrolyzable group other than a        hydroxyl group, a represents 0, 1, 2 or 3, b represents 0, 1 or        2 and m is an integer of 0 to 19 provided that the relation        a+mb≦1 should be satisfied. Among them, those in which m is 0        are preferred.

Y″ is not particularly restricted but includes, among others, ketoximo,acyloxy, alkoxy, amido, aminoxy, amino, alkenoxy and halogen groups anda hydrogen atom. Among them, halogen groups are preferred.

As more specific and preferred examples of such silicon compound, theremay be mentioned dialkylchlorosilanes, in particularchlorodimethylsilane.

The amount of the silicon compound having both a hydrolyzable group anda hydrosilyl group which is to be reacted with the alkenyl-terminatedpolymer is not particularly restricted but, when a compoundhaving onlyone hydrosilyl group is used, the amount thereof may be equivalentrelative to the alkenyl group. When a compound having a plurality ofhydrosilyl groups is used, there is the possibility of coupling thereofby the hydrosilylation reaction and, therefore, the compound ispreferably used in excess.

For causing the hydrosilylation reaction to proceed rapidly, ahydrosilylation catalyst may be added. As such hydrosilylation catalyst,there may be mentioned a radical initiator such as an organic peroxideand an azo compound, and a transition metal catalyst.

The radical initiator is not particularly restricted but may be any ofvarious compounds. As examples, there may be mentioned dialkyl peroxidessuch as di-tert-butyl peroxide,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, dicumyl peroxide, tert-butylcumyl peroxideand α,α′-bis(tert-butylperoxy) isopropylbenzene, diacyl peroxides suchas benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide,2,4-dichlorobenzoyl peroxide and lauroyl peroxide, peresters such astert-butyl perbenzoate, peroxydicarbonates such as diisopropylperoxydicarbonate and di-2-ethylhexyl peroxydicarbonate, andperoxyketals such as 1,1-di(tert-butylperoxy) cyclohexane and1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, among others.

As the transition metal catalyst, there may be mentioned, for example,simple substance platinum, solid platinum dispersed on a support such asalumina, silica and carbon black, chloroplatinic acid, complexes ofchloroplatinic acid with alcohols, aldehydes, ketones or the like,platinum-olefin complexes and platinum(0)-divinyltetramethyldisiloxanecomplex. As examples of the catalyst other than platinum compounds,there may be mentioned RhCl(PPh₃)₃, RhCl₃, RuCl₃, IrCl₃, FeCl₃, AlCl₃,PdCl₂.H₂O, NiCl₂, TiCl₄, etc. These catalysts may be used singly or twoor more of them may be used combinedly. The amount of the catalyst isnot particularly restricted but recommendably is within the range of10⁻¹ to 10⁻⁸ mole, preferably within the range of 10⁻³ to 10⁻⁶ mole, permole of the alkenyl group of the componet (A). When it is less than 10⁻⁸mole, the curing may not proceed to a sufficient extent. Since thehydrosilylation catalyst is expensive, it is recommendable that thiscatalyst is not used in an amount exceeding 10⁻¹ mole.

The hydrosilylation reaction may be conducted without using any solventor in the presence of a solvent. Ordinary organic solvents, such ashydrocarbon solvents, ether solvents and ester solvents, can be used asthe solvent. However, those capable of serving as ligands of transitionmetals, for example amines and phosphines, may possibly lower thecatalytic activity, hence are undesirable, when a transition metalcatalyst is used.

The hydrosilylation reaction temperature is not particularly restrictedbut the reaction is generally carried out at 0 to 250° C., preferably 20to 150° C., most preferably 40 to 120° C. <Hydrolysis Reaction>

The silyl group having a hydrolyzable group at the polymer terminusproduced in the above manner can be hydrolyzed to give a polymer havinga silanol group.

When the hydrolyzable group is a hydrogen, the hydrolysis can beeffected by a method known in the art, which is not restricted, forexample by reacting with a buffer solution in the presence of a Pd/Ccatalyst (J. Org. Chem., 31, 885 (1966)) or by reacting with a buffersolution in the presence of a platinum catalyst.

When the hydrolyzable group is a halogen group, in particular achlorine, the hydrolysis is generally carried out at 0 to 60° C.,preferably in the presence of a base, such as sodium bicarbonate, whichis used for neutralizing the byproduct hydrochloric acid, although theconditions are not limited thereto.

Introduction of a Group Represented by General Formula (1)

The vinyl polymer having a group of the general formula (1) at at leastone terminus according to the present invention can be produced byreacting the vinyl polymer (II) having a silanol group at at least oneterminus as prepared above with a silicone compound represented by thegeneral formula (6);X′SiR″₂-G-C(O)CR¹═CR²R³   (6)

-   -   wherein R¹, R²and R³are as defined hereinbefore; R″ represents a        hydrocarbon group of 1 to 14 carbon atoms or a halogenated        hydrocarbon group of 1 to 10 carbon atoms; the plurality of R″        may be the same or different; X′ represents a hydrolyzable        group; G represents an oxyalkylene group of 1 to 4 carbon atoms.

Referring to the general formula (6) , G is preferably a grouprepresented by a formula selected from the group consisting of —CH₂O—,—CH₂CH₂O—, —CH₂CH₂CH₂O— and —CH₂CH(CH₃)CH₂O—, although these are notexclusive choices.

In this reaction, X′ is a group which may condense with the silanolgroup of polymer (II) to form a siloxane (namely, Si—O—Si) bond and maygive SiOH on hydrolysis. And the compound of the general formula (6) ora hydrolyzate thereof condenses with the SiOH group of polymer (II) toform a siloxane bond. The X′ group is selected from among thehydrolyzable groups mentioned hereinbefore in connection with thesilicon compound having a hydrolyzable group and a hydrosilyl group foruse in the production of polymer (II). X′ is preferably a chlorine.

This reaction is typically conducted in an organic solvent (e.g.tetrahydrofuran (THF), diethyl ether, chloroform, toluene, hexane, or amixture thereof). The reaction temperature suitable for thiscondensation is dependent on the individual species of the X group, forwhile certain X groups are ready to react at room temperature, othersrequire high temperatures or even a condensation catalyst for goingthrough the reaction. The combination required in each case belongs tothe scope of one skilled in the art and the optimum combination can beeasily determined by routine experimentation. X′ is preferably achlorine atom, and the following reaction is carried out generally inthe presence of an acid acceptor, such as pyridine, triethylamine anddibutylamine, in order to neutralize the byproduct hydrochloric acid. Inthe above mode of practice, the preferred reaction temperature is 0 to100° C.

<<Description of the Curable Composition>>

The curable composition which constitutes the second aspect of thepresent invention is now described.

The polymer (I) having at least one group of the general formula (1) atterminus according to the invention may form a curable composition. Sucha curable composition is cured by heat, visible light or ultravioletradiation. When the group represented by general formula (1) is acinnamate group, the polymer may undergo dimerization on exposure tolight or the like even in the absence of a catalyst and, therefore, doesnot essentially call for addition of a catalyst, although, it ispreferable to use a photopolymerization initiator or a thermalpolymerization initiator as the catalyst. Moreover, where necessary, acocatalyst such as a sensitizer may also be used. The same applies tocases where the group represented by general formula (1) is a conjugateddiene group which is capable of crosslinking on heating even in theabsence of a catalyst.

<Photopolymerization Initiator>

The photopolymerization initiator that can be used in the curablecomposition of the invention is not particularly restricted but ispreferably a photoradical initiator or a photoanionic initiator. Forexample, there can be mentioned acetophenone, propiophenone,benzophenone, xanthol, fluorene, benzaldehyde, anthraquinone,triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone,3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone,4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone,4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone,4-chloro-4′-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone,3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butylether, bis (4-dimethylaminophenyl) ketone, benzyl methoxy ketal and2-chlorothioxanthone. These initiators can be used alone or incombination with other compounds. As specific examples, combinationswith an amine such as diethanolmethylamine, dimethylethanolamine,triethanolamine or the like, said combinations further including aniodonium salt such as diphenyliodonium chloride, and combinations with acolorant, e.g. methylene blue, and an amine can be mentioned.

As the near-infrared photopolymerization initiator, cationic dyesabsorbing in the near infrared (IR) region of the spectrum can be used.As such near IR-absorbing cationic dyes, it is preferable to use thenear-IR-absorbing cationic dye-borate anion complexes which are excitedby photoenergy within the range of 650 to 1500 nm as disclosed inJapanese Kokai Publication Hei-3-111402 and Japanese Kokai PublicationHei-5-194619, among others, and it is still more advantageous to use aboron-type sensitizer in combination.

The photopolymerization initiator is used in a sufficient amount toattain the desired curing velocity. When the amount is too small, thecure time is prolonged beyond the acceptable limit. When the amount ofthe photopqlymerization initiator is too large, the physical andmechanical properties of the cured composition are adversely affected.The optimum amount is not restricted but the proportion of thephotopolymerization initiator may range from 0.25 to 0.5 part per 100parts of the polymer (I) of the invention.

In the curable composition of the invention, the photopolymerizationinitiator responds to light, for example UV light, to form a radicalwhich induces the crosslinking reaction of polymer (I). Thus, radicalsgenerated by the UV light, for instance, and the photopolymerizationinitiator react with each other to form a crosslink.

<Thermal Polymerization Initiator>

The thermal polymerization initiator is not particularly restricted butincludes azo compounds, peroxides, persulfates and redox initiators.

Suitable azo initiators include but are not limited to2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33),2,2′-azobis(2-amidinopropane) dihydrochloride (VAZO 50),2,2′-azobis(2,4-dimethylvaleronitrile) (VAZO 52), 2,2′-azobis(isobutyronitrile) (VAZO 64), 2,2′-azobis-2-methylbutyronitrile (VAZO67), 1,1-azobis(1-cyclohexanecarbonitrile) (VAZO 88) (all available fromDuPont Chemical), 2,2′-azobis(2-cyclopropylpropionitrile), and2,2′-azobis(methyl isobutyrate) (V-601) (available from Wako PureChemical Ind.), among others.

Suitable peroxide initiators include but are not limited to benzoylperoxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide,dicetylperoxy dicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate(Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl)diperoxycarbonate, t-butyl peroxypivalate (Lupersol 11) (available fromElf Atochem), t-butyl peroxy-2-ethyl hexanoate (Trigonox 21-C50)(available from Akzo Nobel), and dicumyl peroxide.

Suitable persulfate initiators include but are not limited to potassiumpersulfate, sodium persulfate, and ammonium persulfate.

Suitable redox (oxidation-reduction) initiators include but are notlimited to combinations of said persulfate initiators with a reducingagent such as sodium hydrogen metasulfite and sodium hydrogen sulfite;organic peroxide-tertiary amine systems, e.g. benzoylperoxide-dimethylaniline; and organic hydroperoxide-transition metalsystems, e.g. cumene hydroperoxide-cobalt naphthenate.

Other initiators include but are not limited to pinacols such astetraphenyl-1,1,2,2-ethanediol.

Preferred thermal radical initiators can be selected from among azoinitiators and peroxide initiators. Still more preferred are2,2′-azobis(methyl isobutyrate), t-butyl peroxypivalate,di(4-t-butylcyclohexyl) peroxydicarbonate, and a mixture thereof.

The thermal polymerization initiator in the present invention should beadded in a catalytically effective amount which is not particularlyrestricted but is typically about 0.01 to 5 weight parts, preferablyabout 0.025 to 2 weight parts based on 100 weight parts of the polymerhaving a group of the general formula (1) at at least one terminus andthe other monomer/oligomer combined.

<Monomer/Oligomer>

The curable composition of the present invention is essentiallycomprised of the components mentioned above and for avoiding the odorproblem associated with the residual monomer, preferably does notcontain other polymerizable monomers. However, depending on the intendedapplication, polymerizable monomers and/or oligomers and variousadditives may also be formulated. As such polymerizable monomers and/oroligomers, it is preferable to use monomers and/or oligomers havingradical-polymerizable groups or monomers and/or oligomers havinganion-polymerizable groups. As the radical-polymerizable groups, therecan be mentioned groups of the general formula (I), acrylic functionalgroups such as (meth)acryloyl, styryl, acrylonitrile, vinyl ester,N-vinylpyrrolidone, acrylamide, conjugated diene, vinyl ketone, andvinyl chloride groups, among others. Among these, those having a(meth)acryloyl group similar to the functional group in the polymer ofthe invention are preferred. The anion-polymerizable groups includegroups of the general formula (I) (meth)acryloyl, styryl, acrylonitrile,N-vinylpyrrolidone, acrylamide, conjugated diene, and vinyl ketonegroups, among others. Among these, those having a group of the generalformula (I) or an acrylic functional group are preferred.

As examples of such monomers, there can be mentioned (meth) acrylatemonomers, cyclic acrylates, N-vinylpyrrolidone, styrenic monomers,acrylohitrile, N-vinylpyrrolidone, acrylamide monomers, conjugated dienemonomers and vinyl ketone monomers, among others. The (meth)acrylatemonomers include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,isooctyl (meth)acrylate, isononyl (meth)acrylate, and compounds of thefollowing formulas.

The styrenic monomer includes styrene, α-methylstyrene, etc.; theacrylamide monomer includes acrylamide, N,N-dimethylacrylamide, etc.;the conjugated diene monomer includes butadiene, isoprene, etc.; and thevinyl ketone monomer includes methyl vinyl ketone, among others.

The polyfunctional monomer includes neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxy triacrylate, bisphenol Fpolyethoxy diacrylate, bisphenol A polyethoxy diacrylate,dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxyethyl)isocyanurate polyhexanolide triacrylate, tricyclodecanedimethyloldiacrylate,2-(2-acryloyloxy-1,1-dimethyl)-5-ethyl-5-acryloyloxymethyl-1,3-dioxane,tetrabromobisphenol A diethoxy diacrylate, 4,4-dimercaptodiphenylsulfide dimethacrylate, polytetraethylene glycol diacrylate,1,9-nonanediol diacrylate and ditrimethylolpropane tetraacrylate, amongothers.

The oligomer includes epoxy acrylate resins such as bisphenol A epoxyacrylate resin, phenol novolac epoxy acrylate resin, cresol novolacepoxy acrylate resin, etc., COOH-modified epoxy acrylate resins,urethane acrylate resins obtainable by reacting a hydroxyl-containing(meth)acrylate [e.g. hydroxyethyl (meth) acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, or pentaerythritol triacrylate]with the urethane resin obtained from a polyol (e.g. polytetramethyleneglycol, ethylene glycol-adipic acid polyester diol, {dot over(a)}-caprolactone-modified polyester diols, polypropylene glycol,polyethylene glycol, polycarbonate diols, hydroxy-terminatedhydrogenated polyisoprene, hydroxy-terminated polybutadiene,hydroxy-terminated polyisobutylene, etc.) and an organic isocyanate(e.g. tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc.),and resins synthesized by introducing (meth) acryloyl groups into saidpolyols through ester linkages, and polyester acrylate resins.

Further, as the monomer and/or oligomer to be added, the 3-arylacrylicacid compounds disclosed in Japanese Kohyo Publication Hei-10-508642 arealso preferred.

These monomers and oligomers are selected with reference to thepolymerization initiator and curing conditions to be used.

The number average molecular weight of the acrylic functionalgroup-containing monomer and/or oligomer is preferably not larger than2000 and, from a compatibility point of view, is more preferably notlarger than 1000.

<Additives>

To modify the properties of the curable composition, additionalcomponents can be formulated. The mechanical strength of the curedcomposition can be further increased by adding a reinforcing filler. Thepreferred reinforcing filler includes silica and carbon black, amongothers. Furthermore, extender fillers such as clay and calciumcarbonate; pigments; dyes; thickeners; etc. may also be formulated.

<Curing>

The method of curing the curable composition of the invention is notparticularly restricted. In the case of photocuring, depending on theproperties of the photopolymerization initiator, the composition isirradiated with light or an electron beam using a high-pressure mercuryvapor lamp, low-pressure mercury vapor lamp, electron beam generator,halogen vapor lamp, light-emitting diode, semiconductor laser or thelike.

The UV radiation dose necessary for the crosslinking of thefunctionalized curable composition of the present invention depends onmany variables and, therefore, the optimum dose should be determined byexperimentation. The wavelength of UV light, the density and type ofoptically active functional groups on the organic polymer, the amountand kind of photoinitiator, reactor design and other factors areinvariably relevant to the UV radiation dose necessary for the curing ofthe functionalized polymer.

The method for thermal curing of the curable composition of the presentinvention is not particularly restricted. The temperature to be useddepends on the kinds of thermal initiator, polymer (I) and additivecomponents, etc. but is preferably in the range of 50° C. to 150° C. inordinary cases, more preferably 70° C. to 130° C. The cure time, whichis correlated with the polymerization initiator, monomer, solvent,reaction temperature, etc., is generally 1 minute to 10 hours.

<Use>

Being curable in the above manner, the curable composition of thepresent invention is suitable for use as a surface coating, an adhesiveor a sealant.

Such a coating imparts water-proof to the substrate. The substrate forthis application typically includes metals, e.g. aluminum, steel, ironand brass, masonry materials, e.g. concrete, marble and other stones,cellulosic materials, e.g. paper, cotton, fiber-boards, paperboard,wood, woven and nonwoven fabrics, and plastics, e.g. polycarbonates,among others.

As regards the properties of cured products obtainable from the curablecomposition of the invention, a broad range of products ranging fromrubbery ones to resinous ones can be freely designed according to themolecular weight and main chain structure of the polymer. Therefore, asspecific uses for the curable composition of the invention, there can bementioned sealants, adhesives, self-adhesives, elastic adhesives,coatings, powder coatings, foams, electric/electronic potting materials,film, gaskets, resists, various molding compounds and man-made marble,among others.

BEST MODE FOR CARRYING OUT THE INVENTION

The following examples and comparative examples illustrate the presentinvention in further detail, it being, however, to be understood thatthese examples are by no means definitive of the scope of the invention.

As referred to in the following examples, the “number average molecularweight” and “molecular weight distribution (ratio of weight averagemolecular weight to number average molecular weight)” are the valuesdetermined by gel permeation chromatography (GPC) based on polystyrenestandards. Thus, columns packed with crosslinked polystyrene gels wereused as the GPC columns and chloroform was used as the GPC solvent.

PRODUCTION EXAMPLE 1 Examples of Synthesis of a Br Group-terminatedPoly(butylacrylate)

A 10-L separable flask equipped with a reflux-condenser and a stirrerwas charged with CuBr (28.0 g, 0.20 mol), followed by nitrogen gaspurging. Then, acetonitrile (559 mL) was added and the mixture wasstirred on an oil bath at 70° C. for 40 minutes. Thereafter, butylacrylate (1.00 kg), diethyl 2,5-dibromoadipate (117 g, 0.505 mol) andpentamethyldiethylenetriamine [hereinafter sometimes referred to brieflyas triamine] (1.7 mL, 1.41 g, 8.1 mmol) were added and the reaction wasstarted. Under heating at 70° C. with constant stirring, butyl acrylate(4.00 kg) was continuously added dropwise. In the course of drippingbutyl acrylate, triamine (8.5 mL, 7.06 g, 0.041 mol) was further added.

This reaction mixture was diluted with toluene and passed through anactivated alumina column, and the volatile matter was distilled offunder reduced pressure, whereby a Br group-terminated polymer (polymer[1]) was obtained. This polymer [1] had a number average molecularweight of 19500 and a molecular weight distribution value of 1.17.

EXAMPLE 1 Example of Synthesis of Cinnamate-terminatedPoly(butylacrylate)

A 50-mL reactor was charged with the polymer [1] (10 g) obtained inProduction Example 1, potassium cinnamate (0.38 g, 2.1 mmol) anddimethylacetamide (10 mL), and the charge was stirred under nitrogen at70° C. for 3 hours. After the volatile matter was removed by heatingunder reduced pressure, the residue was diluted with toluene and passedthrough an activated alumina column. The toluene was then distilled offunder reduced pressure to give a cinnamate(—OC(O)—CH═CH—C₆H₅)—terminated poly(butyl acrylate) (polymer [2]). Thepolymer [2] had a number average molecular weight of 20500 and amolecular weight distribution value of 1.19. The average number ofcinnamate groups introduced per molecule of the polymer was 1.8 asdetermined by ¹H NMR analysis.

EXAMPLE 2 Example of Synthesis of Conjuaated Diene-terminatedPoly(butylacrylate)

A 100-mL reactor was charged with the polymer [1] (10 g) obtained inProduction Example 1, potassium sorbate (0.31 g, 2.1 mmol) anddimethylacetamide (10 mL). The charge was stirred under nitrogen at roomtemperature for 24 hours and then stirred with heating at 70° C. for anadditional 2 hours. This reaction mixture was diluted with toluene,passed through an activated alumina column, and washed with water. Theorganic layer was concentrated under reduced pressure to give apoly(butyl acrylate) having the sorbic acid-derived conjugated dienestructure (—OC(O)CH═CH—CH═CH—CH₃) at a terminus (polymer [3]). Thepolymer [3] had a number average molecular weight of 20600 and amolecular weight distribution value of 1.20. The average number ofconjugated diene groups introduced per molecule of the polymer was 2.1as determined by ¹H NMR analysis.

EXAMPLE 3 Example 1 of Production of a Cured Product

The polymer [2] (100 parts) obtained in Example 1 was mixed well withthe organic peroxide Perhexa 3M(1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane; product of NOFCorporation) (2 parts) and the mixture was poured into a reaction vesseland defoamed under reduced pressure. Under nitrogen, the mixture washeated at 150° C. for 5 minutes, whereupon a cured product havingrubber-like elasticity was obtained.

The uncured matter in the cured product was extracted with toluene andthe gel fraction was calculated from the difference in weight of thecured product before and after extraction. The gel fraction was 75%.

EXAMPLE 4 Example 2 of Production of a Cured Product

The polymer [3] (100 parts) obtained in Example 2 was mixed well withthe organic peroxide Perhexa 3M(1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane; product of NOFCorporation) (2 parts) and the mixture was poured into a reaction vesseland defoamed under reduced pressure. Under nitrogen, the mixture washeated at 150° C. for 15 minutes, whereupon a cured product havingrubber-like elasticity was obtained.

The uncured matter in the cured product was extracted with toluene andthe gel fraction was calculated from the difference in weight of thecured product before and after extraction. The gel fraction thus foundwas 95%.

INDUSTRIAL APPLICABILITY

The vinyl polymer having a group represented by the general formula (1)at a terminus contains the reactive function group at a high rate and,as such, can undergo thermal/photocuring so that it can be used withadvantage as a coating material, among other applications. Moreover,since the main chain of the polymer is a vinyl polymer, the curedproduct is highly resistant to weathering. Furthermore, because thefunctional group has been introduced into the polymer terminus, thecured product has rubber-like elasticity, among other characteristics.

1-20. (canceled)
 21. A vinyl polymer having at least one group of thegeneral formula (1) at a molecular chain terminus;-Z-R—CR¹═CR²R³   (1) wherein Z represents an oxygen atom, a sulfur atom,a group of the formula NR′, R′ represents a univalent hydrocarbon groupcontaining 1 to 20 carbon atoms, or a bivalent organic group containing1 to 20 carbon atoms: R represents a carbonyl group, a direct bond or abivalent organic group containing 1 to 20 carbon atoms; R¹ and R² arethe same or different and each represents a hydrogen atom or a univalentorganic group containing 1 to 20 carbon atoms; R³ represents a univalentorganic group containing 1 to 20 carbon atoms; which is obtainable byreacting a vinyl polymer (II) having a silanol group at at least onemolecular chain terminus with a silicon compound of the general formula(6);X′SiR″₂-G-C(O)CR¹═CR²R³   (6) wherein R¹ and R² are the same ordifferent and each represents a hydrogen atom or a univalent organicgroup containing 1 to 20 carbon atoms; R³ represents a univalent organicgroup containing 1 to 20 carbon atoms; R″ represents a hydrocarbon groupcontaining 1 to 14 carbon atoms or a halogenated hydrocarbon groupcontaining 1 to 10 carbon atoms: the plurality of R″ may be the same ordifferent: X′ represents a hydrolyzable group; G represents anoxyalkylene group containing 1 to 4 carbon atoms; and wherein G in thegeneral formula (6) is —CH₂O—, —CH₂CH₂O—, —CH₂CH₂CH₂O— or—CH₂CH(CH₃)CH₂O—.
 22. The polymer according to claim 21 wherein thesilanol group of the vinyl polymer (II) is represented by the generalformula (7); —[Si(R⁵)_(2-b)(OH)_(b)O]_(m)—Si(R⁶)_(3-a)(OH)_(a) whereinR⁵ and R⁶ are the same or different and each represents an alkyl groupcontaining 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbonatoms, an aralkyl group containing 7 to 20 carbon atoms, or atriorganosiloxy group of the formula (R′)₃Si—, where R′ represents aunivalent hydrocarbon group containing 1 to 20 carbon atoms and thethree R′ groups may be the same or different; when R⁵ or R⁶ occurs inthe number of 2 or more, the plurality of groups may be the same ordifferent; a represents 0, 1, 2 or 3; b represents 0, 1 or 2; m is aninteger of 0 to 19; with the condition that the relation of a +mb>1 issatisfied.
 23. The polymer according to claim 22 wherein m in thegeneral formula (7) is equal to
 0. 24. The polymer according to claim 21wherein the vinyl polymer (II) is obtainable by subjecting a vinylpolymer having at least one alkenyl group at a terminus tohydrosilylation reaction with a silicon compound having both ahydrolyzable group linked to a silicon atom and a hydrosilyl group andthen hydrolyzing the hydrolyzable group linked to the silicon atom forconversion to a silanol group.
 25. The polymer according to claim 24wherein the silicon compound having both a hydrolyzable group linked toa silicon atom and a hydrosilyl group is chlorodimethylsilane.
 26. Acurable composition comprising the polymer according to claim
 21. 27.The curable composition according to claim 26 which comprises aphotopolymerization initiator and is capable of curing on exposure tolight or an electron beam.
 28. The curable composition according toclaim 26 which comprises a thermal polymerization initiator and iscapable of curing on heating.
 29. The curable composition according toclaim 26 comprising a monomer and/or oligomer having aradical-polymerizable group.
 30. The curable composition according toclaim 29 wherein the radical-polymerizable group is an acrylicfunctional group.
 31. The curable composition according to claim 30wherein the monomer and/or oligomer having said acrylic functional grouphas a number average molecular weight of not more than
 2000. 32. Thepolymer according to claim 22 wherein the vinyl polymer (II) isobtainable by subjecting a vinyl polymer having at least one alkenylgroup at a terminus to hydrosilylation reaction with a silicon compoundhaving both a hydrolyzable group linked to a silicon atom and ahydrosilyl group and then hydrolyzing the hydrolyzable group linked tothe silicon atom for conversion to a silanol group.
 33. The polymeraccording to claim 23 wherein the vinyl polymer (II) is obtainable bysubjecting a vinyl polymer having at least one alkenyl group at aterminus to hydrosilylation reaction with a silicon compound having botha hydrolyzable group linked to a silicon atom and a hydrosilyl group andthen hydrolyzing the hydrolyzable group linked to the silicon atom forconversion to a silanol group.
 34. The polymer according to claim 32wherein the silicon compound having both a hydrolyzable group linked toa silicon atom and a hydrosilyl group is chlorodimethylsilane.
 35. Thepolymer according to claim 33 wherein the silicon compound having both ahydrolyzable group linked to a silicon atom and a hydrosilyl group ischlorodimethylsilane.
 36. A curable composition comprising the polymeraccording to claim
 22. 37. A curable composition comprising the polymeraccording to claim
 23. 38. A curable composition comprising the polymeraccording to claim
 24. 39. A curable composition comprising the polymeraccording to claim
 25. 40. A curable composition comprising the polymeraccording to claim 50.